TW201940971A - Colored photosensitive resin composition, color filter and image display device using the same capable of implementing the shape of the pattern in the form of a taper before the post-baking process during the color filter manufacturing process - Google Patents
Colored photosensitive resin composition, color filter and image display device using the same capable of implementing the shape of the pattern in the form of a taper before the post-baking process during the color filter manufacturing process Download PDFInfo
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- TW201940971A TW201940971A TW108105169A TW108105169A TW201940971A TW 201940971 A TW201940971 A TW 201940971A TW 108105169 A TW108105169 A TW 108105169A TW 108105169 A TW108105169 A TW 108105169A TW 201940971 A TW201940971 A TW 201940971A
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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
- G03F7/028—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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- 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
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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
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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
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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Abstract
Description
本發明係關於一種著色感光性樹脂組合物、包含該著色感光性樹脂組合物的彩色濾光片及影像顯示裝置。The present invention relates to a colored photosensitive resin composition, a color filter including the colored photosensitive resin composition, and an image display device.
作為利用著色感光性樹脂組合物形成彩色濾光片的方法,主要使用以下方法:在基板或預先形成有期望圖案的遮光層的基板上形成著色感光性樹脂組合物的塗膜,藉由具有預定的圖案的光罩照射光(以下,稱為曝光),顯影而使非曝光部分溶解去除,然後進行後烘烤,從而獲得各個顏色的像素。As a method for forming a color filter using a colored photosensitive resin composition, the following method is mainly used: forming a coating film of a colored photosensitive resin composition on a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance, The patterned mask is irradiated with light (hereinafter referred to as exposure), developed to dissolve and remove non-exposed portions, and then post-baked to obtain pixels of each color.
此外,近年來,在彩色濾光片的技術領域中,為了減少曝光量而縮短產距時間以及為了應對近來要求的影像顯示裝置的高色純度化的要求,趨勢是增加著色感光性樹脂組合物中所佔的著色劑的含量(比例),由此隨著著色劑以外的成分的含量的減少,可能發生製造彩色濾光片時密合性下降、產生殘渣等問題。In addition, in recent years, in the technical field of color filters, in order to reduce the exposure time, to shorten the production time, and to meet the recent requirements for high color purity of image display devices, there is a trend to increase the coloring photosensitive resin composition. As the content (ratio) of the coloring agent in the colorant decreases, the adhesiveness may decrease when the color filter is manufactured, and problems such as residue may occur as the content of components other than the colorant decreases.
對此,韓國註冊專利第10-0875269號揭露了一種彩色濾光片用感光性樹脂組合物及利用該感光性樹脂組合物的彩色濾光片,其特徵在於,上述感光性樹脂組合物包含鹼可溶性樹脂、丙烯酸系光聚合性單體、光聚合引發劑、顏料及溶劑,上述鹼可溶性樹脂為a)特定化學式所表示的包含一個以上的雙鍵的乙烯性不飽和單體、b)具有一個以上的羧基的乙烯性不飽和單體、以及c)能夠與上述b)的單體共聚的乙烯性不飽和單體的共聚物,從而能夠製造沒有殘渣、密合性優異、且由超微小像素組成的高解析度的彩色濾光片,但是,利用這樣的組合物製造彩色濾光片時,具有在後續熱處理製程(後烘烤)前圖案的形狀形成為反斜面形態而製程上產生差錯的問題。In response, Korean Registered Patent No. 10-0875269 discloses a photosensitive resin composition for a color filter and a color filter using the photosensitive resin composition, wherein the photosensitive resin composition contains an alkali A soluble resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent. The alkali-soluble resin is a) an ethylenically unsaturated monomer containing one or more double bonds represented by a specific chemical formula, and b) having one The above carboxyl ethylenically unsaturated monomers and c) copolymers of ethylenically unsaturated monomers that can be copolymerized with the monomers of b) can produce residues, excellent adhesion, and ultrafine Pixels are high-resolution color filters. However, when a color filter is manufactured using such a composition, the shape of the pattern before the subsequent heat treatment process (post-baking) is formed into a reverse-beveled shape and a process error occurs. The problem.
先前技術文獻
專利文獻
專利文獻1:韓國註冊專利第10-0875269號(2018.12.15.)Prior Art Literature Patent Literature Patent Literature 1: Korean Registered Patent No. 10-0875269 (2018.12.15.)
[所要解決的課題][Problems to be solved]
本發明是為了解決如上所述的問題而提出的,其目的在於,提供一種在進行彩色濾光片製造製程中屬於高溫熱處理的後烘烤製程之前能夠將圖案的形狀形成為正斜面的形態從而不產生製程上的問題的著色感光性樹脂組合物、包含該著色感光性樹脂組合物的彩色濾光片及影像顯示裝置。
[解決課題的方法]The present invention has been made in order to solve the above-mentioned problems, and an object thereof is to provide a pattern that can be formed into a shape of a bevel before a post-baking process that belongs to a high temperature heat treatment in a color filter manufacturing process, thereby A colored photosensitive resin composition that does not cause a problem in the manufacturing process, a color filter including the colored photosensitive resin composition, and an image display device.
[Method to solve the problem]
用於實現上述目的之本發明的著色感光性樹脂組合物的特徵在於,包含光聚合引發劑(A),上述光聚合引發劑(A)包含在365奈米之波長處的光吸收率為0.1%以上的光聚合引發劑(a1),上述光聚合引發劑(a1)為下述化學式1或化學式2所表示的化合物,
[化學式1]
[化學式 2]
(上述化學式1及化學式2中,
R1
係各自獨立地由下述化學式3表示,
R2
為烴基,分子量各自獨立地為50至150,
R3
各自獨立地為經取代或未經取代的二苯基硫醚基、經取代或未經取代的咔唑基、經取代或未經取代的茀基)
[化學式3]
(上述化學式3中,
R4
為C1至C8的伸烷基、C6至C20的伸芳基或C7至C25的伸芳烷基,
R5
係各自獨立地為CN、C1至C8的烷基、C3至C8的環結構、C6至C20的芳基或C7至C25的芳烷基)。The colored photosensitive resin composition of the present invention for achieving the above-mentioned object is characterized by including a photopolymerization initiator (A), and the photopolymerization initiator (A) includes a light absorption rate at a wavelength of 365 nm of 0.1. % Or more of a photopolymerization initiator (a1), and the photopolymerization initiator (a1) is a compound represented by the following Chemical Formula 1 or Chemical Formula 2,
[Chemical Formula 1]
[Chemical Formula 2]
(In the above Chemical Formulas 1 and 2,
R 1 is each independently represented by the following Chemical Formula 3,
R 2 is a hydrocarbon group, each of which has a molecular weight of 50 to 150,
R 3 is each independently a substituted or unsubstituted diphenyl sulfide group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group)
[Chemical Formula 3]
(In the above Chemical Formula 3,
R 4 is an alkylene group of C1 to C8, an alkylene group of C6 to C20, or an alkylene group of C7 to C25,
R 5 is each independently CN, C1 to C8 alkyl, C3 to C8 ring structure, C6 to C20 aryl, or C7 to C25 aralkyl).
此外,本發明的彩色濾光片的特徵在於,包含上述的著色感光性樹脂組合物的固化物。Moreover, the color filter of this invention contains the hardened | cured material of the said coloring photosensitive resin composition, It is characterized by the above-mentioned.
此外,本發明的影像顯示裝置的特徵在於,包含上述的彩色濾光片。
[發明效果]The image display device of the present invention includes the above-mentioned color filter.
[Inventive effect]
本發明的著色感光性樹脂組合物具有在彩色濾光片製造製程中的後烘烤製程之前能夠將圖案的形狀形成為正斜面的形狀從而不產生製造製程上的問題等優點。The colored photosensitive resin composition of the present invention has advantages such that the shape of the pattern can be formed into the shape of a positive slope before the post-baking process in the color filter manufacturing process, so that there are no problems in the manufacturing process.
本發明的彩色濾光片具有與上述優點相同的優點。The color filter of the present invention has the same advantages as those described above.
本發明的影像顯示裝置具有與上述優點相同的優點。The image display device of the present invention has the same advantages as those described above.
本發明中,當指出某一構件位於另一構件「上」時,其不僅包含某一構件與另一構件接觸的情況,還包含二構件之間存在有其他構件的情況。In the present invention, when it is indicated that a certain component is "on" another component, it includes not only the case where a certain component is in contact with another component, but also the case where there are other components between the two components.
本發明中,當指出某一部分「包含」某一組成要素時,只要沒有特別相反的記載,則其意思是可進一步包含其他組成要素,而不是將其他組成要素排除。In the present invention, when a certain part “includes” a certain constituent element, as long as there is no particularly contrary description, it means that other constituent elements may be further included instead of excluding other constituent elements.
以下,對本發明進行更詳細說明。Hereinafter, the present invention will be described in more detail.
<< 著色感光性樹脂組合物Colored photosensitive resin composition >>
本發明的一態樣的著色感光性樹脂組合物的特徵在於,包含光聚合引發劑(A),上述光聚合引發劑(A)包含在365奈米之波長處的光吸收率為0.1%以上的光聚合引發劑(a1),上述光聚合引發劑(a1)為下述化學式1或化學式2所表示的化合物,從而能夠在彩色濾光片製造製程中的後烘烤製程之前將圖案的形狀形成為正斜面(taper)的形態,因此具有能夠防止後烘烤完成的最終產品中形成反斜面而產生漏光等不良,且能夠防止所形成的圖案中產生孔(hole)等優點。
[化學式1]
[化學式2]
(上述化學式1及化學式2中,
R1
係各自獨立地由下述化學式3表示,
R2
為烴基,其分子量各自獨立地為50至150,
R3
係各自獨立地為經取代或未經取代的二苯基硫醚基、經取代或未經取代的咔唑基、經取代或未經取代的茀基)
[化學式3]
(上述化學式3中,
R4
為C1至C8的伸烷基、C6至C20的伸芳基或C7至C25的伸芳烷基,
R5
係各自獨立地為CN、C1至C8的烷基、C3至C8的環結構、C6至C20的芳基或C7至C25的芳烷基)。In one aspect of the present invention, the colored photosensitive resin composition includes a photopolymerization initiator (A), and the photopolymerization initiator (A) includes a light absorption rate of 0.1% or more at a wavelength of 365 nm. Photopolymerization initiator (a1), the photopolymerization initiator (a1) is a compound represented by the following Chemical Formula 1 or Chemical Formula 2, so that the shape of the pattern can be formed before the post-baking process in the color filter manufacturing process. Forming a tapered shape (taper) has the advantages of preventing the formation of a reverse bevel in the final product after the post-baking and causing defects such as light leakage, and preventing the formation of holes in the formed pattern.
[Chemical Formula 1]
[Chemical Formula 2]
(In the above Chemical Formulas 1 and 2,
R 1 is each independently represented by the following Chemical Formula 3,
R 2 is a hydrocarbon group, each of which has a molecular weight of 50 to 150,
R 3 is each independently a substituted or unsubstituted diphenyl sulfide group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted fluorenyl group)
[Chemical Formula 3]
(In the above Chemical Formula 3,
R 4 is an alkylene group of C1 to C8, an alkylene group of C6 to C20, or an alkylene group of C7 to C25,
R 5 is each independently CN, C1 to C8 alkyl, C3 to C8 ring structure, C6 to C20 aryl, or C7 to C25 aralkyl).
上述C1至C8的烷基包括直鏈型或支鏈型,例如,包括甲基、乙基、正丙基、異丙基、正丁基、異丁基、三級丁基、正戊基、正己基或正辛基等。The above C1 to C8 alkyl group includes a linear type or a branched type, and for example, includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, N-hexyl or n-octyl, etc.
上述C6至C20的芳基包括苯基、聯苯基、三聯苯基、茋基、萘基、蒽基、菲基或芘基等。The aryl groups of C6 to C20 mentioned above include phenyl, biphenyl, terphenyl, fluorenyl, naphthyl, anthracenyl, phenanthryl or fluorenyl, and the like.
上述C7至C25的芳烷基包括苄基、苯乙基、2-苯基丙烷-2-基、二苯基甲基、三苯基甲基、苯乙烯基或肉桂基等。The C7 to C25 aralkyl group includes benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl, triphenylmethyl, styryl, or cinnamyl.
光聚合引發劑 (A ) Photopolymerization initiator ( A )
本發明的一態樣的著色感光性樹脂組合物的特徵在於,包含光聚合引發劑(A),上述光聚合引發劑(A)包含在365奈米之波長處的光吸收率為0.1%以上的光聚合引發劑(a1),上述光聚合引發劑(a1)為下述化學式1或化學式2所表示的化合物,從而能夠在彩色濾光片製造製程中的後烘烤製程之前將圖案的形狀形成為正斜面(taper)的形態,因此具有能夠防止製造製程中出現問題,且能夠防止所形成的圖案中產生孔(hole)等優點。In one aspect of the present invention, the colored photosensitive resin composition includes a photopolymerization initiator (A), and the photopolymerization initiator (A) includes a light absorption rate of 0.1% or more at a wavelength of 365 nm. Photopolymerization initiator (a1), the photopolymerization initiator (a1) is a compound represented by the following Chemical Formula 1 or Chemical Formula 2, so that the shape of the pattern can be formed before the post-baking process in the color filter manufacturing process. Formed as a taper, it has the advantages of preventing problems in the manufacturing process, and preventing holes from being formed in the formed pattern.
關於上述光聚合引發劑(a1),具有有機化學知識的一般技藝人士可藉由習知的方法合成後使用,或者也可購買市售品來使用。The above-mentioned photopolymerization initiator (a1) can be synthesized and used by a person skilled in the art by a known method, or a commercially available product can be used.
本發明的一實施態樣的著色感光性樹脂組合物可進一步包含上述光聚合引發劑(a1)以外的光聚合引發劑(a2)。The colored photosensitive resin composition according to an aspect of the present invention may further include a photopolymerization initiator (a2) other than the photopolymerization initiator (a1).
此時,可進一步包含的光聚合引發劑(a2)只要能夠使一同包含的鹼可溶性樹脂及上述光聚合性化合物聚合就沒有特別限定,例如,可舉出例如苯乙酮系、苯偶姻系、二苯甲酮系、噻噸酮(thioxanthone)系、三嗪系、肟系、鎓鹽系、硝基苄基甲苯磺酸酯系或苯偶姻甲苯磺酸酯系等。作為本發明的苯乙酮系化合物,較佳為二乙氧基苯乙酮、2-甲基-2-嗎福林基-1-(4-甲基苯硫基)丙烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、二苯乙二酮二甲基縮酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮的低聚物等,更佳為2-甲基-2-嗎福林基-1-(4-甲基苯硫基)丙烷-1-酮。此外,也可將多種苯乙酮系化合物及其他光聚合引發劑組合使用。作為苯乙酮系化合物以外的光聚合引發劑,可舉出照射光而產生活性自由基的活性自由基產生劑、敏化劑、酸產生劑等。作為上述活性自由基產生劑,可舉出苯偶姻系化合物、二苯甲酮系化合物、噻噸酮系化合物、三嗪系化合物或肟系化合物等。作為苯偶姻系化合物,例如,可舉出苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等。作為二苯甲酮系化合物,例如,可舉出二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯-4'-甲基二苯基硫醚、3,3',4,4'-四(三級丁基過氧化羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等。作為噻噸酮系化合物,例如,可舉出2-異丙基噻噸酮、4-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。作為三嗪系化合物,例如,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-(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(ethenyl)]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基(ethenyl)]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基(ethenyl)]-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(ethenyl)]-1,3,5-三嗪等。作為肟系化合物,可舉出2-(鄰苯甲醯肟)-1-[4-(苯硫基)苯基]-1,2-辛二酮、1-(4-甲基磺醯基-苯基)-丁烷-1,2-丁烷-2-肟-O-乙酸酯、1-(4-甲基磺醯基-苯基)-丁烷-1-酮肟-O-乙酸酯、羥基亞胺基-(4-甲基磺醯基-苯基)-乙酸乙酯-O-乙酸酯、羥基亞胺基-(4-甲基磺醯基-苯基)-乙酸乙酯-O-苯甲酸酯等。作為敏化劑,例如,可舉出2,4,6-三甲基苯甲醯二苯基氧化膦、2,2-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、二苯乙二酮、9,10-菲醌、樟腦醌、苯基乙醛酸甲酯、二茂鈦化合物等。作為酸產生劑,例如,可舉出4-羥基苯基二甲基硫鎓對甲苯磺酸鹽、4-羥基苯基二甲基硫鎓六氟銻酸鹽、4-乙醯氧基苯基二甲基硫鎓對甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基硫鎓六氟銻酸鹽、三苯基硫鎓對甲苯磺酸鹽、三苯基硫鎓六氟銻酸鹽、二苯基碘鎓對甲苯磺酸鹽、二苯基碘鎓六氟銻酸鹽等鎓鹽類或硝基苄基甲苯磺酸酯類、苯偶姻甲苯磺酸酯類等。此外,上述化合物中,也有同時產生活性自由基及酸的化合物。例如,上述三嗪系光聚合引發劑也可用作酸產生劑。In this case, the photopolymerization initiator (a2) that can be further included is not particularly limited as long as it can polymerize the alkali-soluble resin and the photopolymerizable compound that are included together, and examples thereof include acetophenone-based and benzoin-based , Benzophenone-based, thioxanthone-based, triazine-based, oxime-based, onium salt-based, nitrobenzyl tosylate-based or benzoin tosylate-based. As the acetophenone-based compound of the present invention, diethoxyacetophenone, 2-methyl-2-morpholinyl-1- (4-methylphenylthio) propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diphendione dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one Oligomers and the like are more preferably 2-methyl-2-morpholinyl-1- (4-methylphenylthio) propane-1-one. A plurality of acetophenone-based compounds and other photopolymerization initiators may be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based compound include an active radical generator, a sensitizer, and an acid generator that generate an active radical upon irradiation with light. Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, a triazine-based compound, or an oxime-based compound. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzophenone-based compound include benzophenone, methyl benzophenonebenzoate, 4-phenylbenzophenone, and 4-benzophenone-4'-methyldiphenyl. Sulfide, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. , 1-chloro-4-propoxythioxanthone, etc. Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4-bis ( Trichloromethyl) -6- (4-methoxynaphthyl) -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) ethenyl] -1,3, 5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like. Examples of the oxime-based compound include 2- (o-benzophenoxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, and 1- (4-methylsulfonyl) -Phenyl) -butane-1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfonyl-phenyl) -butane-1-one oxime-O- Acetate, hydroxyimino- (4-methylsulfonyl-phenyl) -ethyl acetate-O-acetate, hydroxyimino- (4-methylsulfonyl-phenyl)- Ethyl acetate-O-benzoate and the like. Examples of the sensitizer include 2,4,6-trimethylbenzidinediphenylphosphine oxide and 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'- Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, diphenylethylenedione, 9,10-phenanthrenequinone, camphorquinone, phenylethyl Methyl alginate, titaniumcene compound, etc. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyloxyphenyl Dimethylsulfonium p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate Acid salts, onium salts such as diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin tosylate, and the like. In addition, among the above-mentioned compounds, there are also compounds which generate both an active radical and an acid. For example, the above-mentioned triazine-based photopolymerization initiator can also be used as an acid generator.
根據本發明的一實施態樣,上述光聚合引發劑(a1)的含量係相對於包含其的光聚合引發劑(A)全部100重量份可為70至100重量份,較佳可為90重量份以上。在上述光聚合引發劑(a1)的含量滿足上述範圍的情況下,具有能夠更好地形成正斜面形態等優點。According to an aspect of the present invention, the content of the photopolymerization initiator (a1) may be 70 to 100 parts by weight, and preferably 90 parts by weight with respect to 100 parts by weight of the entire photopolymerization initiator (A). More than. In the case where the content of the photopolymerization initiator (a1) satisfies the above range, there is an advantage such that the shape of the front bevel can be better formed.
根據本發明的一實施態樣,上述光聚合引發劑(A)的含量係相對於包含其的著色感光性樹脂組合物中的總固體成分100重量份可為0.1至30重量份,較佳可為0.5至20重量份。在上述光聚合引發劑(A)的含量處於上述範圍內的情況下,具有包含其的著色感光性樹脂組合物係高靈敏度化而縮短曝光時間從而提高生產率,且能夠維持高解析度等優點。According to an embodiment of the present invention, the content of the photopolymerization initiator (A) may be 0.1 to 30 parts by weight based on 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the photopolymerization initiator (A), and may be preferably It is 0.5 to 20 parts by weight. When the content of the photopolymerization initiator (A) is within the above-mentioned range, the coloring photosensitive resin composition system including the photopolymerization initiator (A) has high sensitivity, shortens the exposure time, improves productivity, and can maintain high resolution and the like.
本發明的著色感光性樹脂組合物也可進一步包含光聚合引發助劑。上述光聚合引發助劑有時與光聚合引發劑(A)組合使用,可用於促進被光聚合引發劑(A)引發聚合的光聚合性化合物的聚合。作為上述光聚合引發助劑,可舉出胺系化合物、烷氧基蒽系化合物、噻噸酮系化合物等。作為胺系化合物,例如,可舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸-2-二甲基胺基乙酯、4-二甲基胺基苯甲酸-2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等,其中,較佳為4,4'-雙(二乙基胺基)二苯甲酮。作為烷氧基蒽系化合物,例如,可舉出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。作為噻噸酮系化合物,例如,可舉出2-異丙基噻噸酮、4-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。上述的光聚合引發助劑可單獨或將二種以上組合使用。The colored photosensitive resin composition of the present invention may further include a photopolymerization initiation aid. The photopolymerization initiation adjuvant may be used in combination with the photopolymerization initiator (A), and may be used to promote the polymerization of a photopolymerizable compound that is polymerized by the photopolymerization initiator (A). Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds. Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-methyl Aniline, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamine) Group) benzophenone and the like, and among them, 4,4′-bis (diethylamino) benzophenone is preferred. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2- Ethyl-9,10-diethoxyanthracene and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. , 1-chloro-4-propoxythioxanthone, etc. The photopolymerization initiation aids described above can be used alone or in combination of two or more.
此外,作為上述光聚合引發助劑,也可使用市售的產品,作為市售的光聚合引發助劑,例如,有EAB-F(保土谷化學工業股份有限公司製品)等。作為本發明的著色感光性樹脂組合物中較佳的光聚合引發劑及光聚合引發助劑的組合,可舉出二乙氧基苯乙酮/4,4'-雙(二乙基胺基)二苯甲酮、2-甲基-2-嗎福林基-1-(4-甲基苯硫基)丙烷-1-酮/4,4'-雙(二乙基胺基)二苯甲酮、2-羥基-2-甲基-苯基丙烷-1-酮/4,4'-雙(二乙基胺基)二苯甲酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮/4,4'-雙(二乙基胺基)二苯甲酮、1-羥基環己基苯基酮/4,4'-雙(二乙基胺基)二苯甲酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙烷-1-酮的低聚物/4,4'-雙(二乙基胺基)二苯甲酮、2-苄基-2-二甲基胺基-1-(4-嗎福林基苯基)丁烷-1-酮/4,4'-雙(二乙基胺基)二苯甲酮的組合等,更佳有2-甲基-2-嗎福林基-1-(4-甲基苯硫基)丙烷-1-酮/4,4'-雙(二乙基胺基)二苯甲酮的組合。在如上述那樣同時使用光聚合引發劑(A) 及光聚合引發助劑的情況下,光聚合引發助劑使用量較佳係以每1莫耳之光聚合引發劑(A)計為10莫耳以下,更佳為0.01至5莫耳。In addition, as the photopolymerization initiation aid, a commercially available product can also be used. As a commercially available photopolymerization initiation aid, for example, EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like can be used. Preferred combinations of the photopolymerization initiator and the photopolymerization initiation aid in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamine group). ) Benzophenone, 2-methyl-2-morpholinyl-1- (4-methylphenylthio) propane-1-one / 4,4'-bis (diethylamino) diphenyl Ketone, 2-hydroxy-2-methyl-phenylpropane-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl] propane-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenyl ketone / 4,4 ' -Oligomer of bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one / 4 , 4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one / 4 , 4'-bis (diethylamino) benzophenone, etc., more preferably 2-methyl-2-morpholinyl-1- (4-methylphenylthio) propane-1- Ketone / 4,4'-bis (diethylamino) benzophenone combination. When the photopolymerization initiator (A) and the photopolymerization initiator are used together as described above, the amount of the photopolymerization initiator is preferably 10 mol per 1 mol of the photopolymerization initiator (A). Below the ear, more preferably from 0.01 to 5 moles.
本發明的一實施態樣的著色感光性樹脂組合物除了上述的光聚合引發劑(A)以外還可包含選自由鹼可溶性樹脂、光聚合性化合物、著色劑、溶劑及添加劑所組成的群組中的一種以上。The colored photosensitive resin composition according to an embodiment of the present invention may include, in addition to the photopolymerization initiator (A) described above, a group selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a colorant, a solvent, and an additive. More than one of them.
鹼Alkali 可溶性樹脂Soluble resin
作為上述鹼可溶性樹脂,可舉出例如含羧基單體以及上述含羧基單體及能夠與其共聚的其他單體的共聚物等。Examples of the alkali-soluble resin include a carboxyl group-containing monomer and a copolymer of the carboxyl group-containing monomer and another monomer copolymerizable therewith.
作為上述含羧基單體,可舉出例如不飽和單羧酸或不飽和二羧酸、不飽和三羧酸等分子中具有一個以上的羧基的不飽和多元羧酸等不飽和羧酸等。本文中,作為不飽和單羧酸,可舉出例如丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸等。作為不飽和二羧酸,可舉出例如馬來酸、富馬酸、伊康酸、檸康酸、中康酸等。不飽和多元羧酸也可為酸酐,具體而言,可舉出馬來酸酐、伊康酸酐、檸康酸酐等。此外,不飽和多元羧酸也可為其單(2-甲基丙烯醯氧基烷基)酯,可舉出例如琥珀酸單(2-丙烯醯氧基乙基)酯、琥珀酸單(2-甲基丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-丙烯醯氧基乙基)酯、鄰苯二甲酸單(2-甲基丙烯醯氧基乙基)酯等。此外,不飽和多元羧酸還可為其二末端二羧基聚合物的單(甲基)丙烯酸酯,可舉出例如ω-羧基聚己內酯單丙烯酸酯、ω-羧基聚己內酯單甲基丙烯酸酯等。上述含羧基單體可各自單獨或將二種以上混合使用。Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxyl groups in molecules such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include a mono (2-propenyloxyethyl) succinate and a mono (2 -Methacryl ethoxy ethyl) ester, phthalic acid mono (2-propenyl ethoxy ethyl) ester, phthalic acid mono (2-methacryl ethoxy ethyl) ester, and the like. In addition, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxyl polymer at its two terminals, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethyl Acrylate, etc. Each of the carboxyl group-containing monomers may be used alone or as a mixture of two or more thereof.
作為上述能夠與含羧基單體共聚的其他單體,可舉出包含雙鍵的乙烯性不飽和單體,例如苯乙烯、α-甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、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基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚、茚等芳香族乙烯基化合物;丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸異丁酯、丙烯酸二級丁酯、甲基丙烯酸二級丁酯、丙烯酸三級丁酯、甲基丙烯酸三級丁酯、丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、甲基丙烯酸-2-羥基丙酯、丙烯酸-3-羥基丙酯、甲基丙烯酸-3-羥基丙酯、丙烯酸-2-羥基丁酯、甲基丙烯酸-2-羥基丁酯、丙烯酸-3-羥基丁酯、甲基丙烯酸-3-羥基丁酯、丙烯酸-4-羥基丁酯、甲基丙烯酸-4-羥基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸-2-甲氧基乙酯、甲基丙烯酸-2-甲氧基乙酯、丙烯酸-2-苯氧基乙酯、甲基丙烯酸-2-苯氧基乙酯、甲氧基二伸乙基甲基丙烯酸酯、丙烯酸異莰酯、甲基丙烯酸異莰酯、丙烯酸二環戊二烯酯、甲基丙烯酸二環戊二烯酯、丙烯酸-2-羥基-3-苯氧基丙酯、甲基丙烯酸-2-羥基-3-苯氧基丙酯、甘油單丙烯酸酯、甘油單甲基丙烯酸酯等不飽和羧酸酯類;丙烯酸-2-胺基乙酯、甲基丙烯酸-2-胺基乙酯、丙烯酸-2-二甲基胺基乙酯、甲基丙烯酸-2-二甲基胺基乙酯、丙烯酸-2-胺基丙酯、甲基丙烯酸-2-胺基丙酯、丙烯酸-2-二甲基胺基丙酯、甲基丙烯酸-2-二甲基胺基丙酯、丙烯酸-3-胺基丙酯、甲基丙烯酸-3-胺基丙酯、丙烯酸-3-二甲基胺基丙酯、甲基丙烯酸-3-二甲基胺基丙酯等不飽和羧酸胺基烷基酯類;丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等不飽和羧酸縮水甘油酯類;乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯類;乙烯基甲基醚、乙烯基乙基醚、烯丙基縮水甘油基醚等不飽和醚類;丙烯腈、甲基丙烯腈、α-氯丙烯腈、二氰亞乙烯等氰化乙烯基化合物;丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺、N-2-羥基乙基丙烯醯胺、N-2-羥基乙基甲基丙烯醯胺等不飽和醯胺類;馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等不飽和醯亞胺類;1,3-丁二烯、異戊二烯、氯丁二烯等脂肪族共軛二烯類;聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、聚矽氧烷的聚合物分子鏈的末端具有單丙烯醯基或單甲基丙烯醯基的巨單體類等。這些單體可各自單獨或將二種以上混合使用。Examples of other monomers that can be copolymerized with the carboxyl group-containing monomer include ethylenically unsaturated monomers containing a double bond, such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyl Vinyl toluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-ethylene Aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene; methyl acrylate, methyl Methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate , Isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, methyl methacrylate 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate Ester, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxy methacrylate Ethyl ester, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethyl methacrylate, isoamyl acrylate, isoamyl methacrylate, Dicyclopentadiene acrylate, dicyclopentadiene methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol mono Unsaturated carboxylic acid esters such as acrylate and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethyl acrylate Aminoethyl ester, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate , 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, methacrylic acid Unsaturated carboxylic acid amino alkyl esters such as -3-dimethylaminopropyl ester; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate Esters, vinyl butyrate, vinyl benzoate and other carboxylic acid vinyl esters; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and other unsaturated ethers; acrylonitrile, methacrylonitrile , Α-chloroacrylonitrile, vinyl cyanide and other vinyl compounds; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2- Unsaturated amines such as hydroxyethyl methacrylamide; unsaturated amines such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; 1, 3-dinger , Isoprene, chloroprene and other aliphatic conjugated dienes; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, poly The macromolecules of the polymer chain of the siloxane have a monoacryl group or a monomethacryl group. These monomers can be used individually or in mixture of 2 or more types.
上述鹼可溶性樹脂中的含羧基單體單元的含量相對於鹼可溶性樹脂全部100重量%,以質量分率計通常可為10至50重量%,較佳可為15至40重量%,更佳可為25至40重量%。在含羧基單體單元的含量處於上述範圍內的情況下,對於顯影液的溶解性良好,顯影時能夠正確地形成圖案。The content of the carboxyl group-containing monomer unit in the above-mentioned alkali-soluble resin is generally 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 100% by weight relative to the total amount of the alkali-soluble resin. It is 25 to 40% by weight. When the content of the carboxyl group-containing monomer unit is within the above range, the solubility in the developing solution is good, and a pattern can be accurately formed during development.
作為上述鹼可溶性樹脂,可舉出例如(甲基)丙烯酸/(甲基)丙烯酸甲酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羥基乙酯/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚苯乙烯巨單體共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚甲基(甲基)丙烯酸酯巨單體共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚苯乙烯巨單體共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚甲基(甲基)丙烯酸酯巨單體共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羥基乙酯/(甲基)丙烯酸苄酯/聚苯乙烯巨單體共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羥基乙酯/(甲基)丙烯酸苄酯/聚(甲基)丙烯酸甲酯巨單體共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸苄酯/N-苯基馬來醯亞胺共聚物、(甲基)丙烯酸/琥珀酸單(2-丙烯醯氧基)酯/苯乙烯/(甲基)丙烯酸苄酯/N-苯基馬來醯亞胺共聚物、(甲基)丙烯酸/琥珀酸單(2-丙烯醯氧基乙基)酯/苯乙烯/(甲基)丙烯酸烯丙酯/N-苯基馬來醯亞胺共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/N-苯基馬來醯亞胺/苯乙烯/甘油單(甲基)丙烯酸酯共聚物等。Examples of the alkali-soluble resin include (meth) acrylic acid / (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, and (meth) acrylic acid / (formyl) Base) 2-hydroxyethyl acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ( Methyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / Benzyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, (meth) acrylic acid / -2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / -2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly (meth) acrylate macromonomer copolymer, ( Methacrylic acid / styrene / benzyl (meth) acrylate N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-propenyloxy) succinate / styrene / benzyl (meth) acrylate / N-phenylmaleimide Amine copolymer, (meth) acrylic acid / mono (2-propenyloxyethyl) succinate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, ( (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer and the like.
其中,較佳可使用(甲基)丙烯酸/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/苯乙烯共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/苯乙烯共聚物。Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, and (meth) acrylic acid / (methyl) ) Methyl acrylate copolymer, (meth) acrylic acid / (meth) acrylate / styrene copolymer.
本說明書中,(甲基)丙烯酸酯的意思是丙烯酸酯及(或)甲基丙烯酸酯。In the present specification, (meth) acrylate means acrylate and / or methacrylate.
根據本發明的一實施態樣,上述鹼可溶性樹脂的酸值可為20至200(毫克KOH/公克)。如果酸值處於上述範圍,則顯影液中的溶解性提高,非曝光部分容易溶解且靈敏度增加,結果為曝光部分的圖案在顯影時留下而能夠改善留膜率(film remaining ratio)。本文中,所謂酸值是作為中和丙烯酸系聚合物1公克時所需的氫氧化鉀的量(毫克)而測定的值,通常可使用氫氧化鉀水溶液進行滴定來求得。According to an aspect of the present invention, the acid value of the alkali-soluble resin may be 20 to 200 (mg KOH / g). If the acid value is in the above range, the solubility in the developing solution is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion is left during development, and the film remaining ratio can be improved. Herein, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and it can be generally obtained by titration with an aqueous potassium hydroxide solution.
此外,根據本發明的一實施態樣,上述鹼可溶性樹脂的由凝膠滲透層析(GPC,gel permeation chromatography;將四氫呋喃作為洗滌溶劑)測定的聚苯乙烯換算重量平均分子量(以下,簡稱為「重量平均分子量」)可為3,000至200,000,較佳為5,000至100,000。如果重量平均分子量處於上述範圍內,則可提高硬度,提高留膜率,且顯影液中的非曝光部分的溶解性提高而解析度能夠變佳。In addition, according to an aspect of the present invention, the above-mentioned alkali-soluble resin has a polystyrene-equivalent weight-average molecular weight (hereinafter, referred to as "hereinafter referred to as" the "PC") measured by gel permeation chromatography (GPC) using tetrahydrofuran as a washing solvent. The weight average molecular weight ") may be 3,000 to 200,000, preferably 5,000 to 100,000. When the weight average molecular weight is within the above range, the hardness can be increased, and the film retention rate can be increased. In addition, the solubility of the non-exposed portion in the developing solution is improved, and the resolution can be improved.
根據本發明的一實施態樣,上述鹼可溶性樹脂的含量係相對於包含其的著色感光性樹脂組合物中的總固體成分100重量份可為10至80重量份,較佳可為20至70重量份。在上述鹼可溶性樹脂的含量處於上述範圍內的情況下,能夠形成圖案,且能夠提高解析度及留膜率。According to an aspect of the present invention, the content of the alkali-soluble resin may be 10 to 80 parts by weight, and preferably 20 to 70 parts by weight relative to 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the same. Parts by weight. When the content of the alkali-soluble resin is within the above range, a pattern can be formed, and resolution and film retention can be improved.
光聚合性化合物Photopolymerizable compound
上述光聚合性化合物只要是能夠藉由光的照射透過由光聚合引發劑產生的活性自由基、酸等進行聚合的化合物,本發明中就沒有特別限定,根據官能性基團的個數,可舉出一官能、二官能、三官能以上的多官能聚合性化合物等。The photopolymerizable compound is not particularly limited in the present invention as long as it is a compound that can be polymerized by irradiation of living radicals, acids, and the like generated by the photopolymerization initiator by irradiation of light, and may be based on the number of functional groups. Examples include monofunctional, difunctional, and trifunctional polyfunctional polymerizable compounds.
作為上述一官能聚合性化合物的具體實例,可舉出壬基苯基卡必醇丙烯酸酯、丙烯酸-2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸-2-羥基乙酯、N-乙烯基吡咯啶酮等。Specific examples of the monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and acrylic acid. 2-hydroxyethyl, N-vinylpyrrolidone and the like.
作為上述二官能聚合性化合物的具體實例,可舉出1,6-己二醇(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(丙烯醯氧基乙基)醚、3-甲基戊二醇二(甲基)丙烯酸酯、丁二醇二甲基丙烯酸酯、己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、乙氧基化新戊二醇二丙烯酸酯、丙氧基化新戊二醇二丙烯酸酯等。Specific examples of the difunctional polymerizable compound include 1,6-hexanediol (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butanediol dimethacrylic acid Ester, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, poly Ethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, and the like.
作為上述三官能以上的多官能聚合性化合物的具體實例,可舉出三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(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、甘油丙氧基化三丙烯酸酯、異氰脲酸酯三丙烯酸酯等三官能聚合性化合物;新戊四醇四(甲基)丙烯酸酯、二羥甲基丙烷四(甲基)丙烯酸酯等四官能聚合性化合物;二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等五官能聚合性化合物等。Specific examples of the trifunctional or higher polyfunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, and ethoxylated trimethylol. Trifunctional polymerizable compounds such as propane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, glycerol propoxylated triacrylate, isocyanurate triacrylate ; Tetrafunctional polymerizable compounds such as neopentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dinepentaerythritol Pentafunctional polymerizable compounds such as hexa (meth) acrylate.
其中,上述光聚合性化合物可各自單獨或將二種以上混合使用,具體而言,較佳可使用二官能以上的多官能聚合性化合物,尤其較佳可使用五官能以上的多官能聚合性化合物,但不限定於此。Among these, the photopolymerizable compounds may be used individually or in combination of two or more kinds. Specifically, it is preferable to use a difunctional or more polyfunctional polymerizable compound, and it is particularly preferable to use a pentafunctional or more polyfunctional polymerizable compound. , But not limited to this.
根據本發明的一實施態樣,上述光聚合性化合物的含量係相對於包含其的著色感光性樹脂組合物中的總固體成分100重量份可為5至50重量份,較佳可為7至45重量份。在上述光聚合性化合物的含量處於上述範圍的情況下,具有像素部的強度或平滑性變佳等優點。According to an aspect of the present invention, the content of the photopolymerizable compound may be 5 to 50 parts by weight, and preferably 7 to 50 parts by weight based on 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the photopolymerizable compound. 45 parts by weight. When the content of the photopolymerizable compound is in the above range, there is an advantage that the strength and smoothness of the pixel portion are improved.
著色劑Colorant
上述著色劑係作為可根據彩色濾光片的用途來進行多種多樣的應用的組成,本發明中,對於其種類沒有特別限定。The colorant is a composition that can be used in various applications depending on the use of the color filter. In the present invention, the type is not particularly limited.
上述著色劑可為顏料、染料或天然色素中的任一種,作為上述顏料,可使用染料索引(Colour Index)(由英國染料與色彩師協會(The Society of Dyers and Colourists)出版)中分類為顏料(pigment)的化合物。作為本發明的著色劑,從耐熱性及顯色性優異的方面考慮,較佳可為有機顏料。The colorant may be any one of a pigment, a dye, or a natural pigment. As the pigment, the color index (published by the Society of Dyers and Colourists) can be used as the pigment. (Pigment) compounds. As the coloring agent of the present invention, an organic pigment is preferred in terms of excellent heat resistance and color rendering properties.
作為本發明中可使用的顏料的較佳具體實例,可舉出:
C.I.顏料黃1、C.I.顏料黃3、C.I.顏料黃12、C.I.顏料黃13、C.I.顏料黃14、C.I.顏料黃15、C.I.顏料黃16、C.I.顏料黃17、C.I.顏料黃20、C.I.顏料黃24、C.I.顏料黃31、C.I.顏料黃53、C.I.顏料黃83、C.I.顏料黃86、C.I.顏料黃93、C.I.顏料黃94、C.I.顏料黃109、C.I.顏料黃110、C.I.顏料黃117、C.I.顏料黃125、C.I.顏料黃128、C.I.顏料黃137、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃147、C.I.顏料黃148、C.I.顏料黃150、C.I.顏料黃153、C.I.顏料黃154、C.I.顏料黃166、C.I.顏料黃173、C.I.顏料黃194、C.I.顏料黃214等黃色顏料;
C.I.顏料橙13、C.I.顏料橙31、C.I.顏料橙38、C.I.顏料橙40、C.I.顏料橙42、C.I.顏料橙43、C.I.顏料橙51、C.I.顏料橙55、C.I.顏料橙59、C.I.顏料橙61、C.I.顏料橙64、C.I.顏料橙65、C.I.顏料橙71、C.I.顏料橙73等橙色顏料;
C.I.顏料紅9、C.I.顏料紅97、C.I.顏料紅105、C.I.顏料紅122、C.I.顏料紅123、C.I.顏料紅144、C.I.顏料紅149、C.I.顏料紅166、C.I.顏料紅168、C.I.顏料紅176、C.I.顏料紅177、C.I.顏料紅180、C.I.顏料紅192、C.I.顏料紅209、C.I.顏料紅215、C.I.顏料紅216、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅264、C.I.顏料紅265等紅色顏料;
C.I.顏料藍15、C.I.顏料藍15:3、C.I.顏料藍15:4、C.I.顏料藍15:6、C.I.顏料藍60等藍色顏料;
C.I.顏料紫1、C.I.顏料紫19、C.I.顏料紫23、C.I.顏料紫29、C.I.顏料紫32、C.I.顏料紫36、C.I.顏料紫38等紫色顏料;
C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58等綠色顏料;
C.I.顏料棕23、C.I.顏料棕25等棕色顏料;
C.I.顏料黑1、C.I.顏料黑7等黑色顏料等。As preferable specific examples of the pigment that can be used in the present invention, there may be mentioned:
CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 125, CI Pigment Yellow 128, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 166, CI Pigment Yellow 173, CI Pigment Yellow 194, CI Pigment Yellow 214 and other yellow pigments;
CI Pigment Orange 13, CI Pigment Orange 31, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 42, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 65, CI Pigment Orange 71, CI Pigment Orange 73 and other orange pigments;
CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Red 265 and other red pigments;
CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60 and other blue pigments;
CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38 and other purple pigments;
CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 and other green pigments;
Brown pigments such as CI Pigment Brown 23 and CI Pigment Brown 25;
Black pigments such as CI Pigment Black 1 and CI Pigment Black 7.
其中,較佳可包含選自C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料紅177、C.I.顏料紅209、C.I.顏料紅254、C.I.顏料紫23、C.I.顏料藍15:6及C.I.顏料綠36中的一種以上的顏料。Among them, it may preferably be selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 254, CI Pigment Violet 23, CI Pigment Blue 15: 6 and One or more pigments of CI Pigment Green 36.
上述的有機顏料及無機顏料可各自單獨使用,也可將二種以上混合使用。例如,在形成紅色像素時,含有C.I.顏料紅254及C.I.顏料黃139,在形成綠色像素時,含有C.I.顏料綠58、C.I.顏料黃150或C.I.顏料黃138,在形成藍色像素時,含有C.I.顏料藍15:6,對於提高顏色再現力均是較佳的,但不限定於此。The above-mentioned organic pigments and inorganic pigments may be used individually or in combination of two or more kinds. For example, when red pixels are formed, CI pigment red 254 and CI pigment yellow 139 are included. When green pixels are formed, CI pigment green 58, CI pigment yellow 150, or CI pigment yellow 138 is included. When blue pixels are formed, CI is included. Pigment Blue 15: 6 is better for improving color reproducibility, but it is not limited to this.
上述染料只要具有對於有機溶劑的溶解性就可無限制地使用一種以上。較佳使用既具有對於有機溶劑的溶解性也能夠確保對於鹼顯影液的溶解性以及耐熱性、耐溶劑性等可靠性的染料。作為上述染料,可使用選自具有磺酸或羧酸等的酸性基團的酸性染料、酸性染料與含氮化合物的鹽、酸性染料的磺醯胺體等以及該等之衍生物中的染料,除此以外,也可選擇偶氮系、二苯并哌喃(xanthene)系、酞菁系的酸性染料以及該等之衍生物。作為上述染料,可舉出染料索引 (由英國染料與色彩師協會(The Society of Dyers and Colourists)出版)中分類為染料的化合物,或者染色筆記(色染社)中記載的習知的染料。As long as the dye has solubility in an organic solvent, one or more of them may be used without limitation. It is preferable to use a dye having both solubility in an organic solvent and reliability in solubility in an alkali developing solution, heat resistance, and solvent resistance. As the dye, a dye selected from the group consisting of an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide of the acidic dye, and the like, In addition, azo-based, xanthene-based, phthalocyanine-based acid dyes, and derivatives thereof can also be selected. Examples of the dyes include compounds classified as dyes in the Dye Index (published by The Society of Dyers and Colourists), and conventional dyes described in Dyeing Notes (Dyeing Society).
作為上述染料的具體實例,對於C.I.溶劑染料而言,可舉出:
C.I.溶劑黃4、14、15、21、23、24、38、62、63、68、82、94、98、99、162等黃色染料;
C.I.溶劑紅8、45、49、122、125、130等紅色染料;
C.I.溶劑橙2、7、11、15、26、45、56、62等橙色染料;
C.I.溶劑藍35、37、45、59、67等藍色染料;
C.I.溶劑綠1、3、4、5、7、28、29、32、33、34、35等綠色染料等。As specific examples of the above dyes, for CI solvent dyes, the following may be mentioned:
CI solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 and other yellow dyes;
CI solvent red 8, 45, 49, 122, 125, 130 and other red dyes;
CI solvent orange 2, 7, 11, 15, 26, 45, 56, 62 and other orange dyes;
CI solvent blue 35, 37, 45, 59, 67 and other blue dyes;
CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other green dyes.
此外,對於C.I.酸性染料而言,可舉出:
C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251等黃色染料;
C.I.酸性紅1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、66、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、183、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、418、422、426等紅色染料;
C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173等橙色染料;
C.I.酸性藍1、7、9、15、18、23、25、27、29、40、42、45、51、62、70、74、80、83、86、87、90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、267、278、280、285、290、296、315、324:1、335、340等藍色染料;
C.I.酸性紫6B、7、9、17、19等紫色染料;
C.I.酸性綠1、3、5、9、16、25、27、50、58、63、65、80、104、105、106、109等綠色染料等。Examples of CI acid dyes include:
CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and other yellow dyes;
CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422, 426 and other red dyes;
CI acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 and other orange dyes;
CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335, 340 and other blue dyes;
CI acid violet 6B, 7, 9, 17, 19 and other purple dyes;
CI acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other green dyes.
此外,對於C.I.直接染料而言,可舉出:
C.I.直接黃2、33、34、35、38、39、43、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141等黃色染料;
C.I.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250等紅色染料;
C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等橙色染料;
C.I.直接藍38、44、57、70、77、80、81、84、85、86、90、93、94、95、97、98、99、100、101、106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、252、256、257、259、260、268、274、275、293等藍色染料;
C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等紫色染料;
C.I.直接綠25、27、31、32、34、37、63、65、66、67、68、69、72、77、79、82等綠色染料等。Examples of CI direct dyes include:
CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141 and other yellow dyes;
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and other red dyes;
CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and other orange dyes;
CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and other blue dyes;
CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and other purple dyes;
CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other green dyes.
此外,對於C.I.媒介染料而言,可舉出:
C.I.媒介黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65等黃色染料;
C.I.媒介紅1、2、3、4、9、11、12、14、17、18、19、22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95等紅色染料;
C.I.媒介橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48等橙色染料;
C.I.媒介藍1、2、3、7、8、9、12、13、15、16、19、20、21、22、23、24、26、30、31、32、39、40、41、43、44、48、49、53、61、74、77、83、84等藍色染料;
C.I.媒介紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等紫色染料;
C.I.媒介綠1、3、4、5、10、15、19、26、29、33、34、35、41、43、53等綠色染料等。In addition, CI CI dyes include:
CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and other yellow dyes;
CI Medium Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and other red dyes;
CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes;
CI Media Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84 and other blue dyes;
CI Medium Purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and other purple dyes;
CI media green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other green dyes.
上述著色劑的含量係相對於包含其的著色感光性樹脂組合物中的總固體成分100重量份可為10至70重量份,較佳可為20至60重量份。在上述著色劑的含量處於上述範圍內的情況下,製成彩色濾光片時的色濃度充分,能夠形成機械強度充分的圖案。The content of the colorant may be 10 to 70 parts by weight, and preferably 20 to 60 parts by weight based on 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the colorant. When the content of the colorant is within the above range, the color density when the color filter is made is sufficient, and a pattern with sufficient mechanical strength can be formed.
本發明中,著色感光性組合物的固體成分的意思是去除溶劑後的成分的總和。In the present invention, the solid content of the colored photosensitive composition means the total of the components after the solvent is removed.
上述顏料中的有機顏料根據需要可實施以下處理:使用導入了酸性基團或鹼性基團的顏料衍生物等的表面處理;利用聚合物化合物等的顏料表面的接枝處理;利用硫酸微粒化法(refinement)等的微粒化處理;為了去除雜質而利用有機溶劑或水等的洗滌處理;或利用離子性雜質的離子交換法等的去除處理等。著色劑較佳為粒徑均勻的。在著色劑為顏料的情況下,藉由添加顏料分散劑而實施分散處理,能夠得到顏料在溶液中呈均勻分散狀態的顏料分散液。The organic pigment among the above pigments may be subjected to the following treatments as required: surface treatment using a pigment derivative or the like in which an acidic group or a basic group is introduced; grafting treatment of a pigment surface with a polymer compound or the like; and micronization with sulfuric acid Micronization treatment such as refinement; washing treatment using organic solvents or water to remove impurities; or removal treatment using ion exchange methods such as ionic impurities. The colorant is preferably uniform in particle diameter. When the colorant is a pigment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing a dispersion treatment by adding a pigment dispersant.
上述顏料較佳以其粒徑均勻分散的顏料分散液的形態使用。作為用於使顏料的粒徑均勻分散的方法的一實例,可舉出藉由添加顏料分散劑而進行分散處理的方法等,根據該方法,能夠得到顏料在溶液中呈均勻分散狀態的顏料分散液。The pigment is preferably used in the form of a pigment dispersion liquid in which the particle diameter is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of a pigment, a method of performing a dispersing treatment by adding a pigment dispersant, etc. can be mentioned, and by this method, a pigment dispersion in which a pigment is uniformly dispersed in a solution can be obtained liquid.
作為上述顏料分散劑的具體實例,可舉出陽離子系、陰離子系、非離子系、二性系、聚酯系、聚胺系等的表面活性劑等,該等可各自單獨或將二種以上組合使用。Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These may be used alone or in combination of two or more kinds. Use in combination.
上述顏料分散劑是為了顏料的解凝及維持穩定性而添加的,可無限制地使用本領域通常使用的顏料分散劑。較佳可使用包含BMA(甲基丙烯酸丁酯,butyl methacrylate)或DMAEMA(甲基丙烯酸-N,N-二甲基胺基乙酯,N,N-dimethylamino ethyl methacrylate)的丙烯酸酯系分散劑(以下,稱為丙烯酸系分散劑)。此時,上述丙烯酸系分散劑較佳可應用如韓國公開專利2004-0014311號中提及的藉由活性控制方法製造的分散劑,作為藉由上述活性控制方法製造的丙烯酸酯系分散劑的市售品,可舉出DISPER BYK-2000、DISPER BYK-2001、DISPER BYK-2070、DISPER BYK-2150等,但不限定於此,該等可各自單獨或將二種以上組合使用。The pigment dispersant is added for the purpose of decoagulation of the pigment and maintaining stability, and pigment dispersants commonly used in the art can be used without limitation. An acrylate dispersant (BMA (butyl methacrylate)) or DMAEMA (N, N-dimethylamino ethyl methacrylate) is preferably used. Hereinafter, it is called an acrylic dispersant). At this time, the above-mentioned acrylic dispersant is preferably applicable to a dispersant manufactured by an activity control method as mentioned in Korean Laid-Open Patent No. 2004-0014311 as a market for an acrylic dispersant manufactured by the above-mentioned activity control method. The sales products include, but are not limited to, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. These can be used alone or in combination of two or more kinds.
上述分散劑也可使用上述的丙烯酸系分散劑以外的其他樹脂型的顏料分散劑。作為上述其他樹脂型的顏料分散劑,可舉出習知的樹脂型顏料分散劑,特別是聚氨酯、以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)銨鹽、聚羧酸的銨鹽、聚羧酸的烷基胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含羥基聚羧酸的酯及該等的改性生成物、或具有自由(free)羧基的聚酯與聚(低級伸烷基亞胺)的反應而形成的醯胺或該等的鹽之類的油性分散劑;(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化合物;聚酯;改性聚丙烯酸酯;環氧乙烷/環氧丙烷的加成生成物及磷酸酯等。作為上述樹脂型分散劑的市售品,對於陽離子系樹脂分散劑而言,可舉出例如畢克(BYK)化學公司的商品名: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;路博潤(Lubrizol)公司的商品名:SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10;川研精細化工公司的商品名:HINOACT T-6000、HINOACT T-7000、HINOACT T-8000;味之素公司的商品名:AJISPER PB-821、AJISPER PB-822、AJISPER 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。上述的丙烯酸系分散劑以外的其他樹脂型的顏料分散劑可各自單獨或將二種以上組合使用,也可與丙烯酸系分散劑並用。As the dispersant, a resin-based pigment dispersant other than the acrylic dispersant may be used. Examples of the other resin-based pigment dispersants include conventional resin-based pigment dispersants, and in particular, polyurethane, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamines, polycarboxylic acids, and polycarboxylic acids. (Partial) ammonium salts of acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, esters of hydroxy-containing polycarboxylic acids, and the like An oily dispersant such as amidine or a salt formed by the reaction of a modified product or a polyester having a free carboxyl group with poly (lower alkyleneimine); (meth) acrylic acid- Water-soluble resin or water-soluble polymer compound such as styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Esters; modified polyacrylates; ethylene oxide / propylene oxide addition products and phosphate esters. Examples of commercially available resin-based dispersants include cationic resin dispersants, for example, trade names of BYK Chemical Company: 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; Trade names of Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Trade names of Chuanyan Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T- 8000; Trade names of Ajinomoto: AJISPER PB-821, AJISPER PB-822, AJISPER PB-823; Trade names of Kyoeisha Chemical Company: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and so on. The resin-based pigment dispersant other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, and may be used in combination with the acrylic dispersant.
在上述著色感光性樹脂組合物進一步包含顏料分散劑的情況下,其含量以一起包含的著色劑每1重量份計可為1重量份以下,更佳可為0.05重量份以上0.5重量份以下。如果上述顏料分散劑的使用量處於上述範圍內,則能夠得到均勻分散的狀態的顏料。When the said coloring photosensitive resin composition further contains a pigment dispersing agent, the content may be 1 weight part or less per 1 weight part of the coloring agents contained together, More preferably, it is 0.05 weight part or more and 0.5 weight part or less. When the amount of the pigment dispersant used is within the above range, a pigment in a uniformly dispersed state can be obtained.
溶劑Solvent
本發明的溶劑只要在分散或溶解一起包含的其他組成成分時有效就可無特別限制地使用,較佳可使用例如醚類、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 without particular limitation as long as it is effective in dispersing or dissolving other constituents contained together, and it is preferable to use, for example, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amidines. Wait.
作為上述醚類,例如,可舉出四氫呋喃、四氫吡喃、1,4-二烷、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、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、丙二醇甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲基醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯、苯甲醚、苯***或甲基苯甲醚等。Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene diethylene glycol. Alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate , Methylcelulose acetate, ethylcelulose acetate, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol methyl ether acetate, methoxybutyl Acetate, methoxypentyl acetate, anisole, phenyl ether, or methyl anisole.
作為上述芳香族烴類,例如,可舉出苯、甲苯、二甲苯或均三甲苯等。Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.
作為上述酮類,例如,可舉出丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮或環己酮等。Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. .
作為上述醇類,例如,可舉出甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇或甘油等。Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol.
作為上述酯類,例如,可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、烷基酯類、乳酸甲酯、乳酸乙酯、氧乙酸甲酯、氧乙酸乙酯、氧乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧丙酸甲酯、3-氧丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-氧丙酸甲酯、2-氧丙酸乙酯、2-氧丙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧-2-甲基丙酸甲酯、2-氧-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧丁酸甲酯、2-氧丁酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯或γ-丁內酯等。Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyl acetate. Ethyl acetate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate , Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-oxopropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxopropionate, ethyl 2-oxopropionate, propionic 2-oxopropionate Esters, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Ester, methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methyl propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate 2-oxo-butyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate or γ- butyrolactone.
作為上述醯胺類,例如,可舉出N,N-二甲基甲醯胺或N,N-二甲基乙醯胺等。Examples of the amidoamines include N, N-dimethylformamide and N, N-dimethylacetamide.
作為其他溶劑,例如,可舉出N-甲基吡咯啶酮或二甲基亞碸等。Examples of the other solvents include N-methylpyrrolidone and dimethylsulfinium.
上述的溶劑可各自單獨或將二種以上混合使用,其中,較佳可使用3-乙氧基丙酸乙酯、丙二醇單甲基醚乙酸酯或丙二醇甲基醚,上述溶劑的含量係相對於包含其的著色感光性樹脂組合物全部100重量份可為10至90重量份。如果溶劑的含量處於上述範圍,則具有塗佈著色感光性樹脂組合物時平坦性良好,且形成彩色濾光片時色濃度充分而顯示特性可變佳等優點。The above-mentioned solvents may be used alone or in combination of two or more kinds. Among them, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, or propylene glycol methyl ether is preferably used. The content of the solvents is relatively It may be 10 to 90 parts by weight based on 100 parts by weight of the coloring photosensitive resin composition including the same. When the content of the solvent is in the above range, there are advantages such that the flatness is good when the colored photosensitive resin composition is applied, the color density is sufficient when the color filter is formed, and the display characteristics can be improved.
添加劑additive
上述著色感光性樹脂組合物除了上述的成分以外根據需要還可包含消泡劑、表面活性劑、熱交聯劑、增黏劑、抗氧化劑等添加劑以提高性能。The colored photosensitive resin composition may include additives such as a defoaming agent, a surfactant, a thermal cross-linking agent, a tackifier, and an antioxidant in addition to the above-mentioned components as necessary to improve performance.
上述表面活性劑是能夠提高基板與著色感光性樹脂組合物的密合性的成分,例如,可使用含氟表面活性劑、非離子表面活性劑、陽離子表面活性劑、陰離子表面活性劑及有機矽表面活性劑之類的各種表面活性劑。該等可單獨或二種以上混合使用。The said surfactant is a component which can improve the adhesiveness of a board | substrate and a colored photosensitive resin composition, For example, a fluorine-containing surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone can be used Various surfactants such as surfactants. These can be used alone or in combination of two or more.
作為含氟表面活性劑的具體實例,可舉出MAGAFAC F171、F172、F173、F176、F177、F141、F142、F143、F144、R30、F437、F475、F479、F482、F554、F780及F781(商品名,DIC公司(DIC Corporation)製品);FLUORAD FC430、FC431及FC171(商品名,住友3M有限公司(Sumitomo 3M Limited)製品);SURFLON S-382、SC-101、SC-103、SC-104、SC-105、SC1068、SC-381、SC-383、S393及KH-40(商品名,旭硝子玻璃有限公司(Asahi Glass Co., Ltd.)製品);SOLSPERSE 20000(商品名,路博潤日本有限公司(Lubrizol Japan Limited)製品)等。Specific examples of the fluorine-containing surfactant include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (trade names) , Products of DIC Corporation); FLUORAD FC430, FC431 and FC171 (trade names, products of Sumitomo 3M Limited); SURFLON S-382, SC-101, SC-103, SC-104, SC -105, SC1068, SC-381, SC-383, S393 and KH-40 (trade names, products of Asahi Glass Co., Ltd.); SOLSPERSE 20000 (trade names, Lubrizol Japan Co., Ltd. (Lubrizol Japan Limited) products).
作為非離子表面活性劑的具體實例,可舉出甘油、三羥甲基丙烷及三羥甲基乙烷以及該等的乙氧基化物或丙氧基化物(例如,丙氧基化甘油或乙氧基化甘油);PLURONIC L10、L31、L61、L62、10R5、17R2及25R2以及TETRONIC 304、701、704、901、904及150R1(商品名,巴斯夫(BASF)製品)之類的聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、去水山梨醇脂肪酸酯等。Specific examples of the non-ionic surfactant include glycerol, trimethylolpropane, and trimethylolethane, and ethoxylates or propoxylates such as those (for example, propoxylated glycerol or ethyl acetate). Oxygenated glycerol); polyoxyethylene laurels such as PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2 and TETRONIC 304, 701, 704, 901, 904, and 150R1 (trade names, products of BASF) Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol di Stearate, sorbitan fatty acid ester, etc.
作為陽離子表面活性劑的具體實例,可舉出EFKA-745(商品名,森下有限公司(Morishita & Co., Ltd.)製品)之類的酞菁改性化合物;KP341(商品名,信越化學有限公司(Shin-Etsu Chemical Co., Ltd.)製品)之類的有機矽氧烷聚合物;POLYFLOW No.75、No.90、No.95(商品名,共榮社化學有限公司(Kyoeisha Chemical Co., Ltd.)製品)之類的(甲基)丙烯酸系(共)聚合物;W001(商品名,裕商有限公司(Yusho Co., Ltd.)製品)等。Specific examples of the cationic surfactant include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.); KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) (Shin-Etsu Chemical Co., Ltd.) and other organic silicone polymers; POLYFLOW No. 75, No. 90, No. 95 (trade names, Kyoeisha Chemical Co., Ltd. (Kyoeisha Chemical Co., Ltd.) ., Ltd. products) (meth) acrylic (co) polymers; W001 (trade name, products of Yusho Co., Ltd.), etc.
作為陰離子表面活性劑的具體實例,可舉出W004、W005、W017(商品名,裕商有限公司製品)等。Specific examples of the anionic surfactant include W004, W005, and W017 (trade names, products of Yushang Co., Ltd.) and the like.
作為有機矽表面活性劑的具體實例,可舉出TORAY SILICONE DC3PA、SH7PA、DC11PA、SH21PA、SH28PA、SH29PA、SH30PA及SH8400(商品名,道康寧東麗有限公司(Dow Corning Toray Co., Ltd. )製品);TSF-4440、4300、4445、4460及4452(商品名,邁圖高性能材料有限公司(Momentive Performance Materials Inc.)製品);KP341、KF6001及KF6002(商品名,信越化學有限公司製品);BYK307、323及330(商品名,畢克化學製品)等。Specific examples of the silicone surfactant include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names, products of Dow Corning Toray Co., Ltd.) ); TSF-4440, 4300, 4445, 4460 and 4452 (trade names, products of Momentive Performance Materials Inc.); KP341, KF6001 and KF6002 (trade names, products of Shin-Etsu Chemical Co., Ltd.); BYK307, 323 and 330 (trade names, BYK Chemicals), etc.
上述熱交聯劑在由著色感光性樹脂組合物形成塗膜時能夠使透過UV照射及熱處理的交聯反應順利地發生,是能夠提高耐熱性的成分。例如,可舉出聚丙烯酸酯樹脂、環氧樹脂、酚醛樹脂、三聚氰胺樹脂、有機酸、胺化合物、無水化合物等。The thermal cross-linking agent is a component capable of smoothly causing a cross-linking reaction through UV irradiation and heat treatment when forming a coating film from a colored photosensitive resin composition, and is capable of improving heat resistance. Examples include polyacrylate resins, epoxy resins, phenol resins, melamine resins, organic acids, amine compounds, and anhydrous compounds.
上述增黏劑具有以下優點:能夠提高與可成為基材的無機物,例如矽、氧化矽、氮化矽等矽化合物或金、銅、鋁等金屬的密合性,且能夠提高調節與基材的錐角的能力。例如,可舉出矽烷偶聯劑或硫醇系化合物,較佳可使用矽烷偶聯劑。The above tackifier has the following advantages: it can improve the adhesion with inorganic substances that can be used as a substrate, such as silicon compounds such as silicon, silicon oxide, and silicon nitride, or metals such as gold, copper, and aluminum; and can improve the adjustment and the substrate Ability to taper angle. For example, a silane coupling agent or a thiol-based compound is mentioned, and a silane coupling agent is preferably used.
上述矽烷偶聯劑的種類沒有特別限定,作為具體實例,可舉出γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-環氧丙氧基丙基三烷氧基矽烷、γ-環氧丙氧基丙基烷基二烷氧基矽烷、γ-甲基丙烯醯氧基丙基三烷氧基矽烷、γ-甲基丙烯醯氧基丙基烷基二烷氧基矽烷、γ-氯丙基三烷氧基矽烷、γ-巰基丙基三烷氧基矽烷、β-(3,4-環氧環己基)乙基三烷氧基矽烷、乙烯基三烷氧基矽烷等,較佳為γ-環氧丙氧基丙基三烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷,更佳為γ-環氧丙氧基丙基三烷氧基矽烷。該等可單獨或二種以上混合使用。The type of the silane coupling agent is not particularly limited, and specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyl Trialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkane Dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, ethylene Γ-trialkoxysilane and the like, preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, more preferably γ-propylene oxide Oxypropyltrialkoxysilane. These can be used alone or in combination of two or more.
作為上述抗氧化劑的例子,一般可舉出2-三級丁基苯酚、2,6-二三級丁基苯酚、2,4-二三級丁基苯酚、2-二級丁基苯酚、2,6-二二級丁基苯酚、2,4-二二級丁基苯酚、2-異丙基苯酚、2,6-二異丙基苯酚、2,4-二異丙基苯酚、2-三級辛基苯酚、2,6-二三級辛基苯酚、2,4-二三級辛基苯酚、2-環戊基苯酚、2,6-二環戊基苯酚、2,4-二環戊基苯酚、2-三級丁基-對甲酚、2,6-二三級戊基苯酚、2,4-二三級戊基苯酚、6-三級丁基-鄰甲酚、2,6-二三級十二烷基苯酚、2,4-二三級十二烷基苯酚、2-二級丁基-對甲酚、2,6-二三級辛基苯酚、2,4-二三級辛基苯酚、6-二級丁基-鄰甲酚、2-三級辛基-對甲酚、2-三級十二烷基-對甲酚、2-三級丁基-6-異丙基苯酚、6-三級辛基-鄰甲酚、6-三級十二烷基-鄰甲酚、4,4'-伸丁基雙(3-甲基-6-三級丁基苯酚)、十八烷基-3-(3,5-二三級丁基-4-羥基苯基)丙酸酯、4,4'-伸丁基雙(6-四-丁基-3-甲基苯酚)、4,4'-硫代-雙(3-甲基-6-三級丁基苯酚)、三乙二醇-雙[3-(3-三級丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙[3-(3,5-二三級丁基-4-羥基苯基)丙酸酯]、新戊四醇-四[3-(3,5-二三級丁基-4-羥基苯基)丙酸酯]、1,3,5-三甲基-2,4,6-三(3,5-二三級丁基-4-羥基苄基)苯、2,6-二三級丁基-4-乙基苯酚、2,2'-伸甲基雙(4-甲基-6-三級丁基苯酚)、1,1,3-三(2-甲基-4-羥基-5-三級丁基苯基)丁烷、1,3,5-三(4-羥基苄基)苯及四[伸甲基-3-(3,5'-二三級丁基-4'-羥基苯基丙酸酯)]甲烷等,該等可使用一種或二種以上。Examples of the antioxidant include 2-tertiary-butylphenol, 2,6-tertiary-butylphenol, 2,4-tertiary-butylphenol, 2-tertiary-butylphenol, 2 2,6-di-second butyl phenol, 2,4-di-second butyl phenol, 2-isopropyl phenol, 2,6-diisopropyl phenol, 2,4-diisopropyl phenol, 2- Tertiary octylphenol, 2,6-secondary tertiary octylphenol, 2,4-secondary tertiary octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-bis Cyclopentylphenol, 2-tertiary-butyl-p-cresol, 2,6-tertiary-tertiary pentylphenol, 2,4-tertiary-tertiary pentylphenol, 6-tertiary-butyl-o-cresol, 2 , 6-Di-tertiary dodecylphenol, 2,4-Di-tertiary dodecylphenol, 2-Second-butyl-p-cresol, 2,6-tertiary octylphenol, 2,4 -Di-tertiary octylphenol, 6-secondary butyl-o-cresol, 2-tertiary octyl-p-cresol, 2-tertiary dodecyl-p-cresol, 2-tertiary butyl- 6-isopropylphenol, 6-tertiary octyl-o-cresol, 6-tertiary dodecyl-o-cresol, 4,4'-endethyl bis (3-methyl-6-tertiary Butylphenol), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'- Butylbis (6-tetra-butyl-3-methylphenol), 4,4'-thio-bis (3-methyl-6-tertiarybutylphenol), triethylene glycol-bis [3 -(3-tertiarybutyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-tertiarybutyl-4- Hydroxyphenyl) propionate], neopentaerythritol-tetrakis [3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene, 2,6-di-tertiary-butyl-4-ethylphenol, 2,2'-methylene Bis (4-methyl-6-tertiarybutylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane, 1,3,5 -Tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-tert-butyl-4'-hydroxyphenylpropionate)] methane, etc. Or two or more.
本發明的著色感光性樹脂組合物的製造方法可無限制地使用本領域通常使用的方法,例如,可藉由如下方法來製造。將著色劑預先與溶劑混合並利用珠磨機等分散至著色材料的平均粒徑達到0.2微米以下程度。此時,根據需要可使用顏料分散劑,此外,有時也會配合鹼可溶性樹脂的一部分或全部。在得到的分散液(以下,有時也稱為漆漿)中以達到預定的濃度的方式進一步添加剩餘的鹼可溶性樹脂、光聚合性化合物及光聚合引發劑、添加劑、根據需要使用的其他的成分,根據需要追加的溶劑並進行混合,從而能夠得到目標著色感光性樹脂組合物。The manufacturing method of the colored photosensitive resin composition of this invention can use the method normally used in the field without limitation, For example, it can manufacture by the following method. The colorant is mixed with a solvent in advance and dispersed with a bead mill or the like until the average particle diameter of the coloring material becomes about 0.2 μm or less. In this case, a pigment dispersant may be used as necessary, and part or all of the alkali-soluble resin may be blended. To the obtained dispersion (hereinafter, also sometimes referred to as a paint slurry), the remaining alkali-soluble resin, photopolymerizable compound, photopolymerization initiator, additives, and other necessary ones are further added so as to reach a predetermined concentration. The components can be added with additional solvents and mixed as necessary to obtain the target colored photosensitive resin composition.
<< 彩色濾光片Color filter >>
本發明的其他態樣的彩色濾光片包含上述的著色感光性樹脂組合物的固化物,從而具有在製造製程中的後烘烤步驟之前能夠將圖案的形狀製造成正斜面的形態從而防止製造製程中產生問題,且能夠防止形成圖案時在圖案中產生孔(hole)等優點。The color filter according to another aspect of the present invention includes the cured product of the colored photosensitive resin composition described above, and thus has a shape capable of producing a shape of a bevel before the post-baking step in the manufacturing process, thereby preventing the manufacturing process. In this way, problems can be caused and holes can be prevented from being formed in the pattern when the pattern is formed.
本發明的彩色濾光片可無限制地使用本領域通常使用的製造方法來製造,作為一實例,可參照第1圖至第3圖來進行說明,具體如下。The color filter of the present invention can be manufactured without limitation using a manufacturing method generally used in the art. As an example, the color filter can be described with reference to FIGS. 1 to 3, as follows.
為了利用本發明的著色感光性樹脂組合物來製造彩色濾光片,需要形成著色圖案,為此,將上述著色感光性樹脂組合物進行圖案處理。具體而言,參照第1圖,使由本發明的著色感光性樹脂組合物形成的顏色層11形成於基板10上部。此時,上述基板10的種類沒有特別限定,可為彩色濾光片自身基板,也可為顯示裝置等中彩色濾光片所處的部位。上述基板10可為玻璃板、矽晶圓以及聚醚碸 (poly ether sulfone,PES)、聚碳酸酯(poly carbonate,PC)等塑膠板等。即,上述基板10可為矽(Si)、矽氧化物(SiOx)或玻璃基板,或者可為高分子基板。這樣,為了使由著色感光性樹脂組合物組成的顏色層11形成於基板10上,例如將由溶劑稀釋的著色感光性樹脂組合物藉由旋塗、狹縫式旋塗、狹縫式塗佈、輥塗、噴霧、噴墨方式等塗佈方法而塗佈於基板上,然後使溶劑等揮發性成分揮發。由此,形成由著色感光性樹脂組合物組成的顏色層11,上述顏色層11由著色感光性樹脂組合物的固體成分組成,幾乎不含有揮發性成分。膜面的厚度係依據組合物的黏度、固體成分的濃度、塗佈速度等塗佈條件來確定,在使用本發明的組合物的情況下,可得到厚度為0.5至5微米的顏色層11。In order to manufacture a color filter using the colored photosensitive resin composition of the present invention, it is necessary to form a colored pattern. To this end, the above-mentioned colored photosensitive resin composition is patterned. Specifically, referring to FIG. 1, a color layer 11 formed of the colored photosensitive resin composition of the present invention is formed on the substrate 10. At this time, the type of the substrate 10 is not particularly limited, and may be a substrate of the color filter itself, or a portion where the color filter is located in a display device or the like. The substrate 10 may be a glass plate, a silicon wafer, a plastic plate such as polyether sulfone (PES), polycarbonate (poly carbonate, PC), or the like. That is, the substrate 10 may be a silicon (Si), silicon oxide (SiOx), or glass substrate, or may be a polymer substrate. In this way, in order to form the color layer 11 composed of the colored photosensitive resin composition on the substrate 10, the colored photosensitive resin composition diluted with a solvent is spin-coated, slit-type spin-coated, slit-type applied, The coating method such as roll coating, spraying, and inkjet method is applied to a substrate, and then volatile components such as a solvent are volatilized. Thereby, a color layer 11 composed of a colored photosensitive resin composition is formed. The color layer 11 is composed of a solid component of the colored photosensitive resin composition and contains almost no volatile components. The thickness of the film surface is determined according to the coating conditions such as the viscosity of the composition, the concentration of the solid content, and the coating speed. When the composition of the present invention is used, a color layer 11 having a thickness of 0.5 to 5 microns can be obtained.
接著,參照第2圖,使在基材10上由著色感光性樹脂組合物形成的顏色層11曝露於光30(曝光)。為了曝光,例如將上述顏色層11透過光罩20以預定圖案照射光30。此時,作為光30,通常使用紫外線的g線(波長:436奈米)、h線、i線(波長:365奈米)等。光30按照光罩20的圖案通過。上述光罩20提供在玻璃板的表面上以預定的圖案遮擋光線的遮光層。光30會被遮光層遮擋。沒有提供該遮光層的玻璃板的部分為透過光線的透光部。按照這樣的透光部的圖案,使上述顏色層11曝光。光30的照射量係根據所使用的著色感光性樹脂組合物而進行適當選擇。Next, referring to FIG. 2, the color layer 11 formed of the colored photosensitive resin composition on the substrate 10 is exposed to light 30 (exposure). For exposure, for example, the color layer 11 is irradiated with light 30 in a predetermined pattern through the mask 20. At this time, as the light 30, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. of ultraviolet rays are generally used. The light 30 passes in accordance with the pattern of the mask 20. The photomask 20 described above provides a light-shielding layer that blocks light in a predetermined pattern on the surface of the glass plate. The light 30 is blocked by the light shielding layer. The portion of the glass plate on which the light shielding layer is not provided is a light transmitting portion that transmits light. The color layer 11 is exposed in accordance with such a pattern of the light transmitting portion. The irradiation amount of the light 30 is appropriately selected according to the coloring photosensitive resin composition used.
經上述光30照射的部分與沒有被光30照射的部分相比溶解度顯著變小,二者的溶解度差異極大化,因此利用這樣的差異來進行顯影作業。為了顯影,例如使曝光後的著色感光性樹脂組合物層浸漬於顯影劑。作為顯影劑,使用鹼化合物、比如碳酸鈉、氫氧化鈉、氫氧化鉀、碳酸鉀、四甲基氫氧化銨等的水溶液。參照第3圖,藉由這樣的顯影,將形成於基板10上的顏色層11中沒有被光30照射的光30未照射區域去除。與此相反,經光30照射的光30照射區域殘留而組成著色圖案11R。顯影後,通常用水清洗上述層並乾燥,得到預定的著色圖案11R。此外,乾燥後,也可實施加熱處理。經加熱處理而形成的著色圖案11R發生固化,由此提高機械強度。如此,由於能夠藉由加熱處理提高著色圖案11R的機械強度,因此較佳使用含有固化劑的著色感光性組合物。加熱溫度通常為180℃以上,較佳為200至250℃。The solubility of the portion irradiated with the light 30 is significantly smaller than that of the portion not irradiated with the light 30, and the difference in solubility between the two is extremely large. Therefore, the development is performed using such a difference. For the development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As the developer, an aqueous solution of an alkali compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide, or the like is used. Referring to FIG. 3, the light 30 unirradiated area in the color layer 11 formed on the substrate 10 that is not irradiated with the light 30 is removed by such development. In contrast, the light-irradiated area irradiated with the light 30 remains and forms the colored pattern 11R. After development, the above layer is usually washed with water and dried to obtain a predetermined coloring pattern 11R. After drying, heat treatment may be performed. The colored pattern 11R formed by the heat treatment is cured, thereby improving the mechanical strength. In this way, since the mechanical strength of the colored pattern 11R can be improved by heat treatment, it is preferable to use a colored photosensitive composition containing a curing agent. The heating temperature is usually 180 ° C or higher, and preferably 200 to 250 ° C.
<< 影像顯示裝置Image display device >>
本發明的又一態樣的影像顯示裝置包含上述的彩色濾光片,從而具有製造製程上不發生問題而不良產生少等優點。上述影像顯示裝置具體可舉出液晶顯示器(液晶顯示裝置;LCD,liquid crystal display)、有機EL(電致發光,electroluminescence)顯示器(有機EL顯示裝置)、液晶投影儀、遊戲機用顯示裝置、行動電話等行動終端用顯示裝置、數位相機用顯示裝置、車輛導航用顯示裝置等顯示裝置等,尤其適合彩色顯示裝置。According to another aspect of the present invention, the image display device includes the above-mentioned color filter, and thus has the advantages of no problem in the manufacturing process and less occurrence of defects. Specific examples of the image display device include a liquid crystal display (liquid crystal display), an organic EL (electroluminescence) display (organic EL display), a liquid crystal projector, a display device for a game machine, and a mobile phone. Display devices such as mobile terminal display devices, digital camera display devices, and car navigation display devices are particularly suitable for color display devices.
上述影像顯示裝置可包含如光源等之類的發光裝置、導光板、包含本發明的彩色濾光片的液晶顯示部等之類的通常影像顯示裝置可包含的其他組成,本發明對此沒有限定。The above-mentioned image display device may include other components that can be included in a normal image display device such as a light source such as a light source, a light guide plate, a liquid crystal display including the color filter of the present invention, and the like, and the present invention is not limited thereto. .
以下,為了幫助本發明的理解,提供較佳的實施例,對於本領域的技藝人士而言顯而易見的是,下述實施例僅是例示本發明,在本發明的範疇以及技術思想範圍內可進行各種各樣的變更及修改,當然這樣的變更及修改也屬於隨附的申請專利範圍。以下的實施例及比較例中,只要無特別提及,則表示含量的「%」 及「份」為重量基準。In the following, in order to help the understanding of the present invention and provide preferred embodiments, it is obvious to those skilled in the art that the following embodiments are only examples of the present invention and can be performed within the scope of the present invention and the technical idea. Various changes and modifications, of course, such changes and modifications also fall within the scope of the attached patent application. In the following examples and comparative examples, unless otherwise mentioned, "%" and "parts" indicating content are based on weight.
實施例 及比較例 Examples and Comparative Examples
按照如下述表1的組成及含量進行混合來製造著色感光性樹脂組合物。The colored photosensitive resin composition was manufactured by mixing according to the composition and content as shown in Table 1 below.
[表1]
[化學式5]
[化學式6]
[化學式7]
[化學式8]
[化學式9]
[Table 1]
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 7]
[Chemical Formula 8]
[Chemical Formula 9]
實驗例Experimental example 1.1. 光聚合引發劑的吸收率及Absorption rate of photopolymerization initiator and R2R2 的分子量測定Determination of molecular weight
將上述實施例及比較例中使用的各個光聚合引發劑在丙二醇單甲基醚乙酸酯中按照0.001重量%進行稀釋,利用紫外-可見光光譜儀(UV-VIS Spectrophotometer,型號名:UV-2550,製造公司:島津 (SHIMADZU) 公司)測定在365奈米之波長處的吸收率,並將結果記載於下述表2中,同時計算並記載針對各個光聚合引發劑中本發明的化學式1或2的R2 所對應的部分的分子量。Each photopolymerization initiator used in the above examples and comparative examples was diluted at 0.001% by weight in propylene glycol monomethyl ether acetate, and a UV-VIS Spectrophotometer (model name: UV-2550, Manufacturing company: Shimadzu Corporation) Measured the absorptivity at a wavelength of 365 nanometers, and described the results in Table 2 below, and calculated and described the chemical formula 1 or 2 of the present invention for each photopolymerization initiator. The molecular weight of the moiety corresponding to R 2 .
[表2]
參照上述表2可確認到,本發明的實施例所包含的光聚合引發劑即A-1至A-4的情況下,R2 所對應的部分的分子量以及在365奈米之波長處的光吸收率係包含在本發明揭露的範圍內。With reference to Table 2 above, it can be confirmed that in the case of A-1 to A-4, which are photopolymerization initiators included in the examples of the present invention, the molecular weight of the portion corresponding to R 2 and the light at a wavelength of 365 nm Absorptance is included in the range disclosed in the present invention.
製造例:彩色濾光片的製造Manufacturing example: manufacturing of color filters
將上述實施例及比較例中製造的各個著色感光性樹脂組合物藉由旋塗法塗佈於玻璃基板上,然後放置於加熱板上在100℃的溫度下維持3分鐘而形成薄膜。接著,在上述薄膜上放置具有1微米至50微米的線條/間隙圖案的試驗光罩且將薄膜與試驗光罩的間隔設為100微米而照射紫外線。此時,紫外線光源使用將g、h、i線全部包含的1千瓦(KW,kilowatt)的高壓汞燈,以50毫焦耳/平方公分(mJ/cm2 )的照度進行照射,沒有使用特別的光學過濾器。將上述經紫外線照射的薄膜在pH 10.5的KOH水溶液顯影溶液中浸漬1分鐘進行顯影。將該覆有薄膜的玻璃板使用蒸餾水洗滌後,吹氮氣以進行乾燥,並在220℃的加熱烘箱中加熱30分鐘,從而製造彩色濾光片。上述製造的彩色濾光片的膜厚度為2.0微米。Each of the colored photosensitive resin compositions produced in the above examples and comparative examples was applied to a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Next, a test mask having a line / gap pattern of 1 μm to 50 μm was placed on the film, and the distance between the film and the test mask was set to 100 μm to irradiate ultraviolet rays. At this time, the ultraviolet light source is a high-pressure mercury lamp of 1 kilowatt (KW, kilowatt), which includes all of the g, h, and i lines, and is irradiated with an illumination intensity of 50 millijoules per square centimeter (mJ / cm 2 ). Optical filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution at pH 10.5 for 1 minute for development. The thin-film-coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 30 minutes to produce a color filter. The film thickness of the color filter manufactured above was 2.0 micrometers.
實驗例Experimental example 2.2. 圖案斜面(Pattern bevel tapertaper )形態)form
利用掃描電子顯微鏡(SEM,scanning electron microscope )如第4圖所示測定上述製造例中220℃加熱製程之前的斜面的長度,並將結果記載於下述表3中。A scanning electron microscope (SEM) was used to measure the length of the inclined surface before the 220 ° C. heating process in the manufacturing example as shown in FIG. 4, and the results are shown in Table 3 below.
實驗例Experimental example 3.3. 圖案線寬(靈敏度)評價Evaluation of pattern line width (sensitivity)
使用掃描電子顯微鏡(SEM)測定上述製造例中形成的圖案的線寬。在圖案的線寬測定為光罩的線寬(100微米)以上的情況下,解釋為著色感光性樹脂組合物的靈敏度充分而線寬擴大。此時,將相對於光罩的擴大的線寬(微米)記載於下述表3中。The line width of the pattern formed in the above-mentioned Production Example was measured using a scanning electron microscope (SEM). When the line width of the pattern is measured as the line width (100 micrometers) or more of the photomask, it is interpreted that the sensitivity of the colored photosensitive resin composition is sufficient and the line width is enlarged. At this time, the expanded line width (micrometer) with respect to the photomask is described in Table 3 below.
[表3]
參照上述表3,確認到在滿足本發明的所有條件的實施例1至4的情況下,與至少不滿足本發明的條件之一的比較例1至4的情況相比,靈敏度優異,且能夠形成正斜面形態。With reference to Table 3 above, it was confirmed that in the cases of Examples 1 to 4 satisfying all the conditions of the present invention, the sensitivity was superior to that of Comparative Examples 1 to 4 that did not satisfy at least one of the conditions of the present invention, and was able to Form a positive bevel.
具體而言,在使用本發明揭露的範圍外的R2 的分子量的光聚合引發劑的比較例1、2及4的情況下,可確認到形成反斜面形態而產生製程上的不良,尤其在超過本發明揭露的R2 分子量的範圍的比較例2的情況下,可確認到圖案形成本身是不可能的,在使用在365奈米波長處的吸收率低於本發明揭露的範圍的光聚合引發劑的比較例3的情況下,可確認到同樣形成反斜面形態,靈敏度也不佳。Specifically, in the case of Comparative Examples 1, 2 and 4 using a photopolymerization initiator having a molecular weight of R 2 outside the range disclosed by the present invention, it can be confirmed that a process defect occurs due to the formation of a reverse bevel, especially in In the case of Comparative Example 2 which exceeded the molecular weight range of R 2 disclosed in the present invention, it was confirmed that pattern formation itself was impossible, and the photopolymerization with an absorption rate at a wavelength of 365 nm lower than the range disclosed in the present invention was used. In the case of Comparative Example 3 of the initiator, it was confirmed that the reverse bevel morphology was similarly formed, and the sensitivity was also poor.
10‧‧‧基板10‧‧‧ substrate
11‧‧‧顏色層 11‧‧‧ Color Layer
11R‧‧‧著色圖案 11R‧‧‧Coloring pattern
20‧‧‧光罩 20‧‧‧Mask
30‧‧‧光 30‧‧‧light
第1圖至第3圖是將彩色濾光片的製造製程圖示化的圖1 to 3 are diagrams illustrating a manufacturing process of a color filter.
第4圖是示出用於區分正斜面及反斜面的斜面長度的測定方法的圖。FIG. 4 is a diagram showing a method of measuring the slope length for distinguishing between a forward slope and a reverse slope.
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