TWI534161B - Copolymers, resin compositions and photosensitive comprising thereof, and color filters - Google Patents

Copolymers, resin compositions and photosensitive comprising thereof, and color filters Download PDF

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TWI534161B
TWI534161B TW101112060A TW101112060A TWI534161B TW I534161 B TWI534161 B TW I534161B TW 101112060 A TW101112060 A TW 101112060A TW 101112060 A TW101112060 A TW 101112060A TW I534161 B TWI534161 B TW I534161B
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copolymer
resin composition
acrylate
group
meth
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TW101112060A
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TW201302822A (en
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木下健宏
小森康廣
橋詰純平
西口將司
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昭和電工股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Description

共聚物、含有該共聚物的樹脂組成物、感光性樹脂組成物、及彩色濾光片 Copolymer, resin composition containing the copolymer, photosensitive resin composition, and color filter

本發明關於一種共聚物、含有該共聚物的樹脂組成物及感光性樹脂組成物、以及彩色濾光片。本發明特別是關於一種共聚物，其係作為用以製造裝在有機EL顯示器、液晶顯示裝置、固體拍攝元件的彩色濾光片所使用的材料；一種含有此共聚物的樹脂組成物；一種感光性樹脂組成物；以及一種使用此感光性樹脂組成物所製造的彩色濾光片。 The present invention relates to a copolymer, a resin composition containing the copolymer, a photosensitive resin composition, and a color filter. More particularly, the present invention relates to a copolymer used as a material for manufacturing a color filter mounted on an organic EL display, a liquid crystal display device, or a solid-state imaging device; a resin composition containing the copolymer; a resin composition; and a color filter produced using the photosensitive resin composition.

近年來，從節省資源或能量的觀點看來，可藉由紫外線或電子束等的活性能量射線硬化的感光性樹脂組成物被廣泛使用在各種鍍膜、印刷、塗料、黏著劑等領域。另外，在印刷電路板等的電子材料領域方面，可藉由活性能量射線硬化的感光性樹脂組成物也被使用於阻焊劑或彩色濾光片用光阻等。 In recent years, from the viewpoint of saving resources or energy, photosensitive resin compositions which can be cured by active energy rays such as ultraviolet rays or electron beams are widely used in various fields such as plating, printing, coatings, and adhesives. Further, in the field of electronic materials such as printed circuit boards, a photosensitive resin composition which can be cured by active energy rays is also used for a solder resist or a photoresist for a color filter.

彩色濾光片一般而言是由玻璃基板等的透明基板；形成於透明基板上的紅(R)、綠(G)及藍(B)的畫素；形成在畫素交界的黑色矩陣；及形成於畫素及黑色矩陣上的保護膜所構成。具有這種構成的彩色濾光片，通常是藉由在透明基板上依序形成黑色矩陣、畫素及保護膜而製造。關於畫素及黑色矩陣(以下將畫素及黑色矩陣稱為「著色圖型」)的形成方法有文獻提出各式各樣的製造方法， 而使用感光性樹脂組成物作為光阻，藉由重覆進行塗佈、曝光、顯像及烘烤的光蝕刻工法來製作的顏料/染料分散法，其耐光性或耐熱性等的耐久性優異，可賦予針孔等的缺陷少的著色圖型，因此成為現在的主流。 The color filter is generally a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) pixels formed on the transparent substrate; and a black matrix formed at the boundary of the pixels; It is composed of a protective film formed on a pixel and a black matrix. A color filter having such a configuration is usually produced by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Regarding the formation methods of pixels and black matrices (hereinafter referred to as "coloring patterns" for pixels and black matrices), various methods of manufacturing are proposed in the literature. A pigment/dye dispersion method which is produced by a photolithography method in which coating, exposure, development, and baking are repeated using a photosensitive resin composition as a photoresist, and is excellent in durability such as light resistance and heat resistance. In addition, it is possible to give a color pattern with fewer defects such as pinholes, and thus it is currently the mainstream.

一般而言，光蝕刻工法所使用的感光性樹脂組成物含有鹼可溶性樹脂、反應性稀釋劑、光聚合起始劑、著色劑及溶劑。顏料/染料分散法具有上述優點，但是相反地，由於重覆形成黑色矩陣、R、G、B的圖型，因此作為塗膜的黏結劑的鹼可溶性樹脂就必須具有高耐熱分解性與耐熱黃變性。關於提升耐熱分解性的方法，過去曾經有文獻提出以含有馬來醯亞胺的單體作為共聚合成分的樹脂組成物(例如專利文獻1)等。但是在以含有馬來醯亞胺的單體作為共聚合成分的樹脂組成物的情況，分子中所含的氮原子會導致黃色至黃褐色的著色，使塗膜的透明性惡化。進一步在進行加熱處理後，在硬化時會有發生著色的問題。另外還已知使用含有甲基丙烯酸與甲基丙烯酸苄酯、甲基丙烯酸羥乙酯、甲基丙烯酸丁酯等的丙烯酸系共聚物，然而其耐熱分解性不足，在使圖型固著的加熱步驟中，熱分解物產生氣體釋放出來，會污染基板或裝置而成為問題。 In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment/dye dispersion method has the above advantages, but conversely, since the pattern of the black matrix, R, G, and B is repeatedly formed, the alkali-soluble resin as a binder of the coating film must have high heat decomposition resistance and heat resistance yellow. transsexual. In the method of improving the thermal decomposition resistance, a resin composition containing a monomer containing a maleimide as a copolymerization component (for example, Patent Document 1) has been proposed. However, in the case of a resin composition containing a monomer containing a maleimide as a copolymerization component, the nitrogen atom contained in the molecule causes yellow to yellowish coloration, and the transparency of the coating film is deteriorated. Further, after the heat treatment, there is a problem that coloring occurs at the time of hardening. Further, it is also known to use an acrylic copolymer containing benzyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate or the like. However, the heat-resistant decomposability is insufficient, and the pattern is fixed. In the step, the decomposition gas generated by the thermal decomposition product is released, which may become a problem by contaminating the substrate or the device.

另外，為了提升耐熱黃變性，若採用使用脂環式的甲基丙烯酸環己酯等的丙烯酸共聚物，則耐熱分解性不充分。關於進一步提升圖型化性或感度的手段，有文獻提出使用對異丙苯基苯酚的乙烯氧化物(EO)變性或丙烯氧化 物(PO)變性(甲基)丙烯酸酯(例如專利文獻2、3)。另外，關於液晶配向用突起形成用負型光阻，有文獻提出使用羥乙基化苯基苯酚(甲基)丙烯酸酯(例如專利文獻4)。但是，關於彩色濾光片用的黏結劑，能夠滿足耐熱分解性或耐熱黃變性的物品仍然未完成。 In addition, in order to improve the heat-resistant yellowing, when an acryl-based copolymer such as alicyclic hexyl methacrylate is used, the thermal decomposition resistance is insufficient. Regarding the means for further improving the patterning or sensitivity, there is a literature suggesting the use of p-cumylphenol for ethylene oxide (EO) denaturation or propylene oxidation. (PO) denatured (meth) acrylate (for example, Patent Documents 2 and 3). In addition, as for the negative-type photoresist for forming a projection for liquid crystal alignment, it has been proposed to use hydroxyethylated phenylphenol (meth)acrylate (for example, Patent Document 4). However, as for the binder for the color filter, an article which can satisfy the heat-resistant decomposition property or the heat-resistant yellowing property is still not completed.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本特開2003-29018號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-29018

專利文獻2：日本特開2004-101728號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-101728

專利文獻3：日本特開2006-215452號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-215452

專利文獻4：日本特開2009-109879號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-109879

如上述所述般，以往的感光性樹脂組成物會有感度或顯像性不足的情形，或無法得到耐熱分解性及耐熱黃變性優異的著色圖型的情形。 As described above, the conventional photosensitive resin composition may have insufficient sensitivity or developability, or may not have a color pattern having excellent heat decomposition resistance and heat yellowing resistance.

所以，本發明為了解決如上述般的課題而完成，目的為提供一種作為感光性樹脂的共聚物，其感度或顯像性良好，同時可賦予耐熱分解性及耐熱黃變性優異的著色圖型；含有其之樹脂組成物及感光性樹脂組成物。另外目的為提供一種彩色濾光片，其係具有耐熱分解性及耐熱黃變性優異的著色圖型。 Therefore, the present invention has been made to solve the problems as described above, and an object of the invention is to provide a copolymer of a photosensitive resin which is excellent in sensitivity and developability, and which can provide a coloring pattern excellent in thermal decomposition resistance and heat yellowing resistance; A resin composition and a photosensitive resin composition containing the same. Another object of the invention is to provide a color filter which has a coloring pattern excellent in heat decomposition resistance and heat yellow resistance.

本發明人等，為了解決如上述般的課題潛心檢討的結果，發現藉由將特定的共聚物使用於感光性樹脂組成物，可解決上述課題，而完成本發明。 The inventors of the present invention have found that the above-described problems can be solved by using a specific copolymer in a photosensitive resin composition as a result of the above-mentioned problem.

亦即，本發明，係[1]一種共聚物(A)，其係使碳數10~20之具有橋接環式烴基之聚合性單體(a-1)及/或下述化學式(1)所表示之聚合性單體(a-1’)與下述化學式(2)所表示之聚合性單體(a-2)聚合而成，且重量平均分子量(聚苯乙烯換算之重量平均分子量)為1000~50000： (式(1)中之X及Y各自獨立，表示氫原子、可為直鏈或分支之碳數1~4之烴基，R1及R2各自獨立，為氫原子、羧基、或可具有取代基之碳數1~20之烴基，亦可採取將R1及R2連結的環狀構造)。 That is, the present invention is a copolymer (A) which is a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and/or the following chemical formula (1) The polymerizable monomer (a-1') and the polymerizable monomer (a-2) represented by the following chemical formula (2) are polymerized, and the weight average molecular weight (weight average molecular weight in terms of polystyrene) For 1000~50000: In the (Formula (1) X and Y each independently represents a hydrogen atom, a straight-chain carbon atoms, unbranched hydrocarbon, or 1 to 4 of, R & lt 1 and R 2 are each independently a hydrogen atom, a carboxyl group, or may have a substituent The hydrocarbon group having 1 to 20 carbon atoms may be a cyclic structure in which R 1 and R 2 are bonded to each other.

(式(2)中之R3表示氫原子或甲基且n表示1~4之整數)。 (R 3 in the formula (2) represents a hydrogen atom or a methyl group and n represents an integer of 1 to 4).

另外，本發明為：[2]如[1]之共聚物(A)，其中含有羧基，酸價為20~300KOHmg/g，[3]如[1]或[2]之共聚物(A)，其中含有不飽和基，[4]如[1]~[3]之任一者之共聚物(A)，其中前述碳數10~20之具有橋接環式烴基之聚合性單體(a-1)含有選自二環戊烯基(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯之至少1種，[5]如[1]~[4]之任一者之共聚物(A)，其中進一步使具有乙烯性不飽和基的自由基聚合性單體(a-3)聚合而成，[6]如[5]之共聚物(A)，其係以前述聚合性單體(a-1)及/或(a-1’)以莫耳比而計為2~50%，前述聚合性單體(a-2)為10~80%，前述聚合性單體(a-3)為18~88%的比例聚合，[7]如[5]或[6]之共聚物(A)，其中前述具有乙烯性不飽和基的自由基聚合性單體係選自不飽和一元酸、不飽和多元酸酐、或縮水甘油基(甲基)丙烯酸酯之1種或2種以上，[8]一種樹脂組成物，其係含有如[1]~[7]之任一者 之共聚物(A)及溶劑(B)，[9]如[8]之樹脂組成物，其中進一步含有反應性稀釋劑(C)，[10]一種感光性樹脂組成物，其係含有如[1]~[7]之任一者之共聚物(A)、溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)，[11]如[10]之感光性樹脂組成物，其中進一步含有由染料及/或顏料所構成之著色劑(E)，[12]如[11]之感光性樹脂組成物，其係彩色濾光片用感光性樹脂組成物，[13]一種彩色濾光片，其係使含有如[12]之感光性樹脂組成物的光阻塗膜硬化而成。 Further, the present invention is: [2] a copolymer (A) according to [1], which contains a carboxyl group, an acid value of 20 to 300 KOHmg/g, [3] a copolymer of [1] or [2] (A) [4] The copolymer (A) according to any one of [1] to [3], wherein the above-mentioned polymerizable monomer having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms (a- 1) Containing at least one selected from the group consisting of dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate, [ [5] The copolymer (A) according to any one of [1] to [4], wherein a radically polymerizable monomer (a-3) having an ethylenically unsaturated group is further polymerized, [6] The copolymer (A) according to [5], wherein the polymerizable monomer (a-1) and/or (a-1') is 2 to 50% in terms of a molar ratio, and the polymerizable monomer ( A-2) is 10 to 80%, the polymerizable monomer (a-3) is polymerized in a ratio of 18 to 88%, and [7] is a copolymer (A) according to [5] or [6], wherein the aforementioned The radically polymerizable single system of the ethylenically unsaturated group is one or more selected from the group consisting of an unsaturated monobasic acid, an unsaturated polybasic acid anhydride, and a glycidyl (meth) acrylate, [8] a resin composition. Any of which system contains of [1] to [7] The one The copolymer (A) and the solvent (B), [9] wherein the resin composition of [8] further contains a reactive diluent (C), [10] a photosensitive resin composition containing, for example, [ The copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D) of any of 1] to [7], [11] the photosensitive resin of [10] The composition further comprising a coloring agent (E) composed of a dye and/or a pigment, [12] a photosensitive resin composition according to [11], which is a photosensitive resin composition for a color filter, [13] A color filter obtained by curing a photoresist coating film containing the photosensitive resin composition of [12].

依據本發明可提供一種共聚物，其感度或顯像性良好，同時可形成耐熱分解性及耐熱黃變性優異的硬化塗膜；或一種含有此共聚物的感光性樹脂組成物。另外，由本發明之感光性樹脂組成物所形成的硬化塗膜，其耐熱性與感度優異，具有顯像性，因此在各種光阻領域的利用價值極高，其中還可提供一種彩色濾光片，其係具有耐熱分解性及耐熱黃變性優異的著色圖型。 According to the present invention, it is possible to provide a copolymer which is excellent in sensitivity or developability and which can form a cured coating film excellent in thermal decomposition resistance and heat yellow resistance, or a photosensitive resin composition containing the copolymer. In addition, the cured coating film formed of the photosensitive resin composition of the present invention is excellent in heat resistance and sensitivity, and has developability. Therefore, it is highly valuable in various photoresist fields, and a color filter can also be provided. It is a coloring pattern excellent in heat decomposition resistance and heat yellow resistance.

首先針對本發明之共聚物(A)作說明。 First, the copolymer (A) of the present invention will be described.

本發明之共聚物(A)，係使碳數10~20之具有橋接環式烴基之聚合性單體(a-1)及/或化學式(1)所表示之聚合性單體(a-1’)與化學式(2)所表示之聚合性單體(a-2)聚合而成，且重量平均分子量(聚苯乙烯換算之重量平均分子量)為1000~50000。 The copolymer (A) of the present invention is a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having a carbon number of 10 to 20 and/or a polymerizable monomer represented by the chemical formula (1) (a-1) ') The polymerizable monomer (a-2) represented by the chemical formula (2) is polymerized, and the weight average molecular weight (weight average molecular weight in terms of polystyrene) is from 1,000 to 50,000.

(式(1)中之X及Y各自獨立，表示氫原子、可為直鏈或分支之碳數1~4之烴基，R1及R2各自獨立，而為氫原子、羧基或可具有取代基之碳數1~20之烴基，亦可採取將R1及R2連結的環狀構造)。 (X and Y in the formula (1) are each independently and represent a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 4 which may be a straight chain or a branched group, and R 1 and R 2 are each independently a hydrogen atom, a carboxyl group or may have a substitution. hydrocarbon group having a carbon number of 1 to 20, the annular structure may take the R 1 and R 2 link).

(式(2)中之R3表示氫原子或甲基且n表示1~4之整數)。 (R 3 in the formula (2) represents a hydrogen atom or a methyl group and n represents an integer of 1 to 4).

構成共聚物(A)的聚合性單體(a-1)係具有碳數10~20之橋接環式烴基。此處，橋接環式烴意指金剛烷、降莰烷所代表的具有下述式(3)或(4)所表示之構造的物質，橋接環式烴基是指相當於將該構造中的一部分的 氫除去之後殘餘的部分的基團。 The polymerizable monomer (a-1) constituting the copolymer (A) has a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms. Here, the bridged cyclic hydrocarbon means a substance represented by adamantane or norbornane having a structure represented by the following formula (3) or (4), and a bridged cyclic hydrocarbon group means a part equivalent to the structure. of The remaining part of the group after hydrogen removal.

(式(3)中，A1、B1分別表示直鏈或分支伸烷基(包括環式)，R4表示氫原子或甲基。A1、B1可相同或相異，A1、B1之分枝可彼此相連而成為環狀)。 (In the formula (3), A 1 and B 1 each represent a linear or branched alkyl group (including a cyclic formula), and R 4 represents a hydrogen atom or a methyl group. A 1 and B 1 may be the same or different, and A 1 , Branches of B 1 may be connected to each other to form a ring).

(式(4)中，A2、B2、L分別表示直鏈或分支伸烷基(包括環式)，R5表示氫原子或甲基。A2、B2、L可相同或相異，A2、B2、L之分枝可彼此相連而成為環狀)。 (In the formula (4), A 2 , B 2 , and L each represent a linear or branched alkyl group (including a cyclic formula), and R 5 represents a hydrogen atom or a methyl group. A 2 , B 2 , and L may be the same or different. The branches of A 2 , B 2 , and L may be connected to each other to form a ring shape).

單體(a-1)係以碳數10~20之具有橋接環式烴基之(甲基)丙烯酸酯為佳，具有(甲基)丙烯酸金剛烷酯或下述式(5)所表示之構造的(甲基)丙烯酸酯為較佳。 The monomer (a-1) is preferably a (meth) acrylate having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms, and has an adamantyl (meth) acrylate or a structure represented by the following formula (5). The (meth) acrylate is preferred.

(式(5)中，R6~R8分別表示氫原子或甲基。R9、R10為氫原子或甲基、或可互相連結形成飽和或不飽和之環、該環宜為5員環或6員環。 (In the formula (5), R 6 to R 8 each independently represent a hydrogen atom or a methyl group. R 9 and R 10 are a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring, and the ring is preferably 5 members. Ring or 6-member ring.

＊表示連結於(甲基)丙烯酸酯基的鍵結鍵)。 * indicates a bonding bond to a (meth) acrylate group).

上述單體(a-1)的例子可列舉(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯等。該等之中，從耐熱分解性、密著性、顯像性等的觀點看來，係以甲基丙烯酸二環戊酯為更佳。該等可單獨或組合兩種以上來使用。 Examples of the monomer (a-1) include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. Wait. Among these, dicyclopentanyl methacrylate is more preferable from the viewpoints of heat decomposition resistance, adhesion, and development properties. These may be used alone or in combination of two or more.

另外，本發明之共聚物(A)其他的構成單體可使用下述一般式(1) (式中，X及Y各自獨立，表示氫原子、或碳數1~4之直鏈或支鏈烴基，R1及R2各自獨立，表示氫原子、羧基或可具有取代基之碳數1~20之烴基，R1及R2可形成連結的環狀構造)。 Further, the other constituent monomer of the copolymer (A) of the present invention can be used in the following general formula (1). (Wherein, X and Y each independently represents a hydrogen atom, or a C 1-4 straight-chain or branched hydrocarbon group having 1 to 4 of, R & lt 1 and R 2 each independently represent a hydrogen atom, a carboxyl group or having a carbon substituent group of having 1 a hydrocarbon group of ~20, and R 1 and R 2 may form a linked cyclic structure).

單體(a-1’)只要具有一般式(1)所表示之化學構 造，則不受到特別限定。在一般式(1)之中，表示碳數1~4之直鏈或支鏈烴基的X及Y的例子可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等。另外，可具有取代基之碳數1~20之烴基中的取代基可列舉烷氧基、芳香基等。R1及R2的例子可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂醯基、月桂基、2-乙基己基等的直鏈或支鏈之烷基；苯基等的芳香基；環己基、第三丁基環己基、二環戊二烯基、三環癸基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等的脂環式基；1-甲氧基乙基、1-乙氧基乙基等的經烷氧基取代的烷基；苄基等的經芳香基取代的烷基等。 The monomer (a-1') is not particularly limited as long as it has a chemical structure represented by the general formula (1). In the general formula (1), examples of X and Y which represent a straight or branched hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutylene. Base, third butyl, etc. Further, examples of the substituent in the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include an alkoxy group and an aromatic group. Examples of R 1 and R 2 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a third pentyl group, a stearyl group, a lauryl group, and 2 a linear or branched alkyl group such as an ethylhexyl group; an aromatic group such as a phenyl group; a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecyl group, an isobornyl group, and an adamantane; An alicyclic group such as 2-methyl-2-adamantyl; an alkoxy-substituted alkyl group such as 1-methoxyethyl or 1-ethoxyethyl; An aryl group-substituted alkyl group or the like.

具有一般式(1)所表示之化學構造的單體(a-1’)的例子可列舉降莰烯(雙環[2.2.1]庚-2-烯)、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、四環[4.4.0.12,5.17,10]十二-3-烯、8-甲基四環[4.4.0.12,5.17,10]十二-3-烯、8-乙基四環[4.4.0.12,5.17,10]十二-3-烯、二環戊二烯、三環[5.2.1.02,6]癸-8-烯、三環[5.2.1.02,6]十二-3-烯、三環[4.4.0.12,5]十一-3-烯、三環[6.2.1.01,8]十一-9-烯、三環[6.2.1.01,8]十一-4-烯、四環[4.4.0.12,5.17,10.01,6]十二-3-烯、8-甲基四環[4.4.0.12,5.17,10.01,6]十二-3-烯、8-亞乙基四環[4.4.0.12,5.17,12]十二-3-烯、8-亞乙基四環[4.4.0.12,5.17,10.01,6]十二-3-烯、五環[6.5.1.13,6.02,7.09,13]十五-4-烯、五環[7.4.0.12,5.19,12.08,13]十五-3-烯、5-降莰烯-2-羧酸、5-降 莰烯-2,3-二羧酸、5-降莰烯-2,3-二羧酸酐等。該等之中，從耐熱分解性、密著性、顯像特性等的觀點看來，係以降莰烯、二環戊二烯、5-降莰烯-2,3-二羧酸酐為佳。該等可單獨或組合兩種以上使用。 Examples of the monomer (a-1') having a chemical structure represented by the general formula (1) include norbornene (bicyclo[2.2.1]hept-2-ene) and 5-methylbicyclo[2.2.1. Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-methyltetra Ring [4.4.0.1 2,5 .1 7,10 ] dode -3-ene, 8-ethyltetracyclo [4.4.0.1 2,5 .1 7,10 ] dode -3-ene, dicyclopentane Diene, tricyclo[5.2.1.0 2,6 ]癸-8-ene, tricyclo[5.2.1.0 2,6 ]dodec-3-ene, tricyclo[4.4.0.1 2,5 ] eleven-3 - alkene, tricyclo[6.2.1.0 1,8 ]undec-9-ene, tricyclo[6.2.1.0 1,8 ]und-4-ene, tetracyclo[4.4.0.1 2,5 .1 7, 10 .0 1,6 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodec-3-ene, 8-ethylene Tetracyclo[4.4.0.1 2,5 .1 7,12 ] dode -3-ene, 8-ethylene tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]12- 3-ene, pentacyclic [6.5.1.1 3,6 .0 2,7 .0 9,13 ] fifteen-4-ene, pentacyclic [7.4.0.1 2,5 .1 9,12 .0 8,13 15-15-3-ene, 5-nordecene-2-carboxylic acid, 5-northene-2,3-dicarboxylic acid, 5-northene-2,3-dicarboxylic anhydride, and the like. Among these, from the viewpoints of heat decomposition resistance, adhesion, development characteristics and the like, it is preferably decene, dicyclopentadiene or 5-northene-2,3-dicarboxylic anhydride. These may be used alone or in combination of two or more.

本發明之必須構成單體是採用下述化學式(2)所表示之聚合性單體(a-2)。 The essential constituent monomer of the present invention is a polymerizable monomer (a-2) represented by the following chemical formula (2).

(式(2)之R3表示氫原子或甲基且n表示1~4之整數)。 (R 3 in the formula (2) represents a hydrogen atom or a methyl group and n represents an integer of 1 to 4).

聚合性單體(a-2)並未受到特別限定，亦可為一般式中之n=1~4的混合物，而為了得到所希望的耐熱分解性，以一般式中n=1的乙氧基化鄰苯基苯酚(甲基)丙烯酸酯為佳。市售品存在有東亞合成股份有限公司製的Aronix TO-1463、新中村化學工業股份有限公司製的NK ester A-LEN-10，日本化藥股份有限公司製的KAYARAD OPP-1等。 The polymerizable monomer (a-2) is not particularly limited, and may be a mixture of n=1 to 4 in the general formula, and in order to obtain a desired thermal decomposition resistance, an ethoxylate of n=1 in the general formula is used. The ortho-phenylphenol (meth) acrylate is preferred. Aronix TO-1463 manufactured by Toagosei Co., Ltd., NK ester A-LEN-10 manufactured by Shin-Nakamura Chemical Co., Ltd., KAYARAD OPP-1 manufactured by Nippon Kayaku Co., Ltd., and the like are commercially available.

另外，關於其他單體，亦可使(a-1)、(a-1’)及(a-2)以外的可共聚合的單體(a-3)進行聚合。聚合性單體(a-3)一般而言具有乙烯性不飽和基的自由基聚合性化合物，其例子可列舉丁二烯等的二烯類；(甲基)丙烯 酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸甲基環己酯、(甲基)丙烯酸乙基環己酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸松香酯、(甲基)丙烯酸降莰酯、(甲基)丙烯酸5-甲基降莰酯、(甲基)丙烯酸5-乙基降莰酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸1,1,1-三氟乙酯、(甲基)丙烯酸全氟乙酯、(甲基)丙烯酸全氟正丙酯、(甲基)丙烯酸全氟異丙酯、(甲基)丙烯酸三苯甲酯、(甲基)丙烯酸異丙苯酯、(甲基)丙烯酸3-(N,N-二甲基胺基)丙酯、甘油單(甲基)丙烯酸酯、丁三醇單(甲基)丙烯酸酯、戊三醇單(甲基)丙烯酸酯、萘(甲基)丙烯酸酯、蒽(甲基)丙烯酸酯等的(甲基)丙烯酸酯類；(甲基)丙烯酸醯胺、(甲基)丙烯酸N,N-二甲基醯胺、(甲基)丙烯酸N,N-二乙基醯胺、(甲基)丙烯酸N,N-二丙基醯胺、(甲基)丙烯酸N,N-二異丙基醯胺、(甲基)丙烯酸蒽基醯胺等的(甲基)丙烯酸醯胺；(甲基)丙烯酸醯苯胺、(甲基)丙烯醯基腈、 丙烯醛、氯化乙烯基、氯化亞乙烯、氟化乙烯基、氟化亞乙烯、N-乙烯基吡咯烷酮、乙烯基吡啶、醋酸乙烯基、乙烯基甲苯等的乙烯基化合物；苯乙烯、苯乙烯之α-、o-、m-、p-烷基、硝基、氰基、醯胺衍生物；檸康酸二乙基、馬來酸二乙基、富馬酸二乙基、伊康酸二乙基等的不飽和二羧酸二酯；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-月桂基馬來醯亞胺、N-(4-羥苯基)馬來醯亞胺等的單馬來醯亞胺類；(甲基)丙烯酸、巴豆酸、桂皮酸等的不飽和一元酸；縮水甘油基(甲基)丙烯酸酯、具有脂環式環氧結構的3,4-環氧環己基甲基(甲基)丙烯酸酯及其內酯加成物[例如DAICEL化學工業股份有限公司製Cyclomer-A200、M100]、3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯之單(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯之環氧化物、(甲基)丙烯酸二環戊烯氧基乙酯之環氧化物等的具有環氧基的自由基聚合性單體：馬來酸酐、伊康酸酐、檸康酸酐等的不飽和多元酸酐。該等可單獨或組合兩種以上使用。 Further, the other monomer may be polymerized with the copolymerizable monomer (a-3) other than (a-1), (a-1') and (a-2). The polymerizable monomer (a-3) generally has a radically polymerizable compound having an ethylenically unsaturated group, and examples thereof include a diene such as butadiene; (meth) propylene; Methyl ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, dibutyl (meth)acrylate, ( Isobutyl methacrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate Ester, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, ( Methyl)cyclohexyl acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, (methyl) Acrylic rosin ester, decyl (meth) acrylate, 5-methyl decyl (meth) acrylate, 5-ethyl decyl (meth) acrylate, allyl (meth) acrylate, ( Methyl)tetrahydrofuran methyl acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, (meth)acrylic acid Perfluoroisopropyl ester, triphenylmethyl (meth)acrylate, (A) Phenylphenyl acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, glycerol mono(meth)acrylate, butyl triol mono(meth)acrylate, pentyl (meth)acrylates such as triol mono(meth)acrylate, naphthalene (meth)acrylate, decyl (meth)acrylate; (meth)acrylic acid decylamine, (meth)acrylic acid N, N-dimethyl decylamine, N,N-diethyl decylamine (meth) acrylate, N,N-dipropyl decylamine (meth) acrylate, N,N-diisopropyl (meth) acrylate (Meth)acrylic acid decylamine such as mercaptoamine or (meth)acrylic acid decylamine; (methyl)acrylic acid anilide, (meth) acrylonitrile nitrile, a vinyl compound of acrolein, vinyl chloride, vinyl chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, etc.; styrene, benzene Alpha-, o-, m-, p-alkyl, nitro, cyano, decylamine derivatives of ethylene; diethyl citraconic acid, diethyl maleate, diethyl fumarate, Ikon Unsaturated dicarboxylic acid diester such as diethyl acid; N-phenylmaleimide, N-cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyl a monomaleimide such as phenyl)maleimide; an unsaturated monobasic acid such as (meth)acrylic acid, crotonic acid or cinnamic acid; glycidyl (meth) acrylate having an alicyclic formula; Epoxy-structured 3,4-epoxycyclohexylmethyl (meth) acrylate and its lactone adducts (for example, Cyclomer-A200, M100 manufactured by DAICEL Chemical Industry Co., Ltd.), 3,4-epoxy ring Mono(meth)acrylate of hexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, bicyclo(meth)acrylate Epoxidation of pentenyloxyethyl ester The radically polymerizable monomer having an epoxy group such as a substance: an unsaturated polybasic acid anhydride such as maleic anhydride, itaconic anhydride or citraconic anhydride. These may be used alone or in combination of two or more.

本共聚物(A)為了提升顯像性係以具有羧基為佳。使羧基加成在共聚物(A)的手段可列舉使具有羧基的單體作為聚合性單體(a-3)而進行共聚合。進一步為了提高感光性，使具有環氧基的單體加成在此羧基的一部分而導入雙鍵亦為佳。或者，亦可先使具有環氧基的單體作為聚合性單體(a-3)進行共聚合，然後加成具有羧基的單體，使酸酐加成在所產生的羥基，而藉此加成羧基與雙鍵 。或者，亦可使不飽和多元酸酐作為聚合性單體(a-3)進行共聚合，使具有羥基的單體加成在此酸酐，而藉此加成羧基與雙鍵。 The copolymer (A) preferably has a carboxyl group in order to enhance the development. The means for adding a carboxyl group to the copolymer (A) is a copolymerization of a monomer having a carboxyl group as a polymerizable monomer (a-3). Further, in order to improve the photosensitivity, it is also preferred to add a monomer having an epoxy group to a part of the carboxyl group to introduce a double bond. Alternatively, the monomer having an epoxy group may be copolymerized as a polymerizable monomer (a-3), and then a monomer having a carboxyl group may be added to add an acid anhydride to the generated hydroxyl group, thereby adding Carboxyl group and double bond . Alternatively, the unsaturated polybasic acid anhydride may be copolymerized as the polymerizable monomer (a-3), and a monomer having a hydroxyl group may be added to the acid anhydride to thereby form a carboxyl group and a double bond.

單體(a-1)與單體(a-1’)可使用其中一者或可使用兩者，而將其一起表示為「單體(a-1)及/或單體(a-1’)」，關於使用量，若設定為意指其全體，則單體(a-1)及/或單體(a-1’)的摻合比例並無特別限制，而在將單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)的合計定為100莫耳%的情況，宜為2~50莫耳%，較佳為2~30莫耳%。若單體(a-1)及/或單體(a-1’)的摻合比例未達2莫耳%，則可能會無法得到所希望的耐熱黃變性。另一方面，若此摻合比例超過50莫耳%，則單體(a-2)的摻合比例變少，可能會無法得到所希望的耐熱分解性。 One of the monomer (a-1) and the monomer (a-1') may be used or both may be used, and they are collectively referred to as "monomer (a-1) and/or monomer (a-1). ')", the amount of use of the monomer (a-1) and/or the monomer (a-1') is not particularly limited, and the monomer is used. The total of a-1) and/or monomer (a-1'), monomer (a-2), and polymerizable monomer (a-3) is set to 100% by mole, preferably 2 to 50 moles. Ear %, preferably 2 to 30 mole %. If the blending ratio of the monomer (a-1) and/or the monomer (a-1') is less than 2 mol%, the desired heat yellowing resistance may not be obtained. On the other hand, when the blending ratio exceeds 50 mol%, the blending ratio of the monomer (a-2) becomes small, and the desired thermal decomposition resistance may not be obtained.

另外，單體(a-2)的摻合比例並無特別限制，而在將單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)之合計定為100莫耳%的情況，宜為10~80莫耳%，較佳為20~70莫耳%。若單體(a-2)的摻合比例未達10莫耳%，則可能會無法得到所希望的耐熱分解性。另一方面，若此摻合比例超過80莫耳%，則單體(a-1)及/或單體(a-1’)摻合比例變少，可能會無法得到所希望的耐熱黃變性。 Further, the blending ratio of the monomer (a-2) is not particularly limited, but the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and the polymerizability. The total of the monomers (a-3) is set to 100 mol%, preferably 10 to 80 mol%, preferably 20 to 70 mol%. If the blending ratio of the monomer (a-2) is less than 10 mol%, the desired thermal decomposition resistance may not be obtained. On the other hand, if the blending ratio exceeds 80 mol%, the blending ratio of the monomer (a-1) and/or the monomer (a-1') becomes small, and the desired heat-resistant yellowing may not be obtained. .

加入單體(a-3)的情況，其摻合比例並無特別限制，而在將單體(a-1)及/或單體(a-1’)、單體(a-2) 以及聚合性單體(a-3)之合計定為100莫耳%的情況，宜為18~88莫耳%，較佳為25~70莫耳%。單體(a-3)的摻合比例為18莫耳%以上的情況，對於進一步提高顯像性、感度而言是有效果的。另一方面，若此摻合比例超過88莫耳%，則單體(a-1)及/或單體(a-1’)、單體(a-2)的摻合比例變少，可能會無法得到所希望的耐熱分解性、耐熱黃變性。 In the case where the monomer (a-3) is added, the blending ratio thereof is not particularly limited, and the monomer (a-1) and/or the monomer (a-1') and the monomer (a-2) are used. When the total of the polymerizable monomers (a-3) is 100 mol%, it is preferably 18 to 88 mol%, preferably 25 to 70 mol%. When the blending ratio of the monomer (a-3) is 18 mol% or more, it is effective for further improving the developability and sensitivity. On the other hand, if the blending ratio exceeds 88 mol%, the blending ratio of the monomer (a-1) and/or the monomer (a-1') and the monomer (a-2) becomes small, possibly The desired thermal decomposition resistance and heat yellowing resistance cannot be obtained.

使用單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)(任意)作為原料的共聚合反應，可依照在該技術領域之中周知的自由基聚合方法來進行。例如只要使單體(a-1)及/或單體(a-1’)、單體(a-2)以及任意單體溶於溶劑之後，在此溶液中添加聚合起始劑，在50~130℃下反應1~20小時即可。 The copolymerization reaction using the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and the polymerizable monomer (a-3) (optional) as a raw material can be carried out according to A radical polymerization method well known in the art is carried out. For example, if the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and any monomer are dissolved in a solvent, a polymerization initiator is added to the solution at 50 The reaction can be carried out at ~130 ° C for 1 to 20 hours.

此共聚合反應可使用的溶劑並未受到特別限定，而可列舉例如丙二醇單甲醚、丙二醇單甲醚醋酸酯等的甘醇醚系溶劑；甲苯、二甲苯等的烴系溶劑、醋酸乙酯等的不具有反應性官能基的溶劑。該等可單獨或組合兩種以上使用。另外，該等之中，甘醇醚系溶劑為佳。 The solvent to be used in the copolymerization reaction is not particularly limited, and examples thereof include a glycol ether solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate; a hydrocarbon solvent such as toluene or xylene; and ethyl acetate. A solvent that does not have a reactive functional group. These may be used alone or in combination of two or more. Further, among these, a glycol ether solvent is preferred.

溶劑的摻合量，並未受到特別限定，而在將單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)之合計定為100質量份的情況，一般而言為30~1000質量份，宜為50~800質量份。特別是藉由將溶劑的摻合量設定在1000質量份以下，可藉由鏈轉移作用來抑制共聚物分子量的降低，且可將共聚物之黏度控制在適 當的範圍。另外，藉由將溶劑的摻合量設定在30質量份以上，可防止異常的聚合反應，且可安定地進行聚合反應，同時還可防止共聚物的著色或膠體化。 The blending amount of the solvent is not particularly limited, and the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and the polymerizable monomer (a-3) are used. In the case where the total amount is 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, by setting the blending amount of the solvent to 1000 parts by mass or less, the molecular weight of the copolymer can be suppressed by chain transfer, and the viscosity of the copolymer can be controlled to be suitable. When the scope. In addition, by setting the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, and the polymerization reaction can be carried out stably, and the coloring or colloidalization of the copolymer can be prevented.

另外，此共聚合反應可使用的聚合起始劑並未受到特別限定，而可列舉例如偶氮雙異丁腈、偶氮雙異戊腈、過氧化苯甲醯、第三丁基過氧-2-乙基已酸酯等。該等可單獨或組合兩種以上使用。 Further, the polymerization initiator which can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, and t-butylperoxy- 2-ethylhexanoate and the like. These may be used alone or in combination of two or more.

關於聚合起始劑的摻合量，在將單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)之合計定為100質量份的情況，一般而言為0.5~20質量份，宜為1.0~10質量份。 Regarding the blending amount of the polymerization initiator, the total of the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and the polymerizable monomer (a-3) In the case of 100 parts by mass, it is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass.

此外，亦可不使用有機溶劑，而使用單體(a-1)及/或單體(a-1’)、單體(a-2)以及聚合性單體(a-3)(任意)與聚合起始劑進行塊狀聚合。 Further, the monomer (a-1) and/or the monomer (a-1'), the monomer (a-2), and the polymerizable monomer (a-3) (optional) may be used without using an organic solvent. The polymerization initiator is subjected to bulk polymerization.

在上述共聚合反應所得到的共聚物(A)中存在羧基、環氧基或酸酐基的情況，可進一步導入雙鍵。藉此可提升感光性樹脂組成物的感度或顯像性。 In the case where a carboxyl group, an epoxy group or an acid anhydride group is present in the copolymer (A) obtained by the above copolymerization reaction, a double bond can be further introduced. Thereby, the sensitivity or developability of the photosensitive resin composition can be improved.

使雙鍵加成在共聚物(A)中的羧基、環氧基或酸酐基的反應，只要在共聚物中分別添加含環氧基的單體、含羧基的單體、含羥基的單體與聚合禁止劑及觸媒，在50~150℃，宜為80~130℃進行反應即可。此外，在此加成反應中，即使含有共聚合反應所使用的溶劑，也並沒有特別的問題，因此在共聚合反應結束之後，不需要將溶劑除去即可進行加成反應。 The double bond is added to the reaction of the carboxyl group, the epoxy group or the acid anhydride group in the copolymer (A) as long as the epoxy group-containing monomer, the carboxyl group-containing monomer, and the hydroxyl group-containing monomer are separately added to the copolymer. It can be reacted with a polymerization inhibitor and a catalyst at 50 to 150 ° C, preferably 80 to 130 ° C. Further, in this addition reaction, even if the solvent used in the copolymerization reaction is contained, there is no particular problem. Therefore, after the completion of the copolymerization reaction, the addition reaction can be carried out without removing the solvent.

另外，此處還可使用上述聚合性單體(a-3)所列舉的化合物。 Further, the compounds exemplified above for the polymerizable monomer (a-3) can also be used herein.

此處添加聚合禁止劑是為了防止共聚物的聚合造成膠體化。聚合禁止劑並未受到特別限定，而可列舉例如氫醌，甲基氫醌、氫醌單甲醚等。另外，觸媒並未受到特別限定，而可列舉例如三乙胺般的3級胺、三乙基苄基銨氯化物般的4級銨鹽、三苯膦般的磷化合物、鉻的螯合化合物等。 The polymerization inhibitor is added here to prevent colloidalization of the polymerization of the copolymer. The polymerization inhibiting agent is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether and the like. Further, the catalyst is not particularly limited, and examples thereof include a tertiary amine such as triethylamine, a tertiary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, and a chelate of chromium. Compounds, etc.

如上述方式所得到的共聚物(A)之酸價(JIS K 6901 5.3)並無限制，而在使用感光性樹脂的情況，通常為20~300KOHmg/g，宜為30~200KOHmg/g。若此酸價未達20KOHmg/g，則會有作為感光性樹脂的顯像性降低的情形。另一方面，若此酸價超過300KOHmg/g，則會有曝光部分(光硬化部分)容易溶於鹼顯像液的情形。 The acid value (JIS K 6901 5.3) of the copolymer (A) obtained as described above is not limited, and in the case of using a photosensitive resin, it is usually 20 to 300 KOH mg/g, preferably 30 to 200 KOH mg/g. When the acid value is less than 20 KOHmg/g, the development property as a photosensitive resin may be lowered. On the other hand, when the acid value exceeds 300 KOHmg/g, there is a case where the exposed portion (photohardened portion) is easily dissolved in the alkali developing solution.

另外，共聚物(A)之分子量(聚苯乙烯換算之重量平均分子量)通常為1000~50000，宜為3000~40000。若此分子量未達1000，則會有在顯像後容易發生著色圖型缺損的情形。另一方面，若此分子量超過50000，則顯像時間變得過長，會有缺乏實用性的情形。 Further, the molecular weight (weight average molecular weight in terms of polystyrene) of the copolymer (A) is usually from 1,000 to 50,000, preferably from 3,000 to 40,000. If the molecular weight is less than 1,000, there is a case where a coloring pattern defect is likely to occur after development. On the other hand, if the molecular weight exceeds 50,000, the development time becomes too long and there is a lack of practicality.

另外，共聚物(A)具有不飽和基的情況，其不飽和基當量並無限制，而通常為100~4000g/mol，宜為200~3000g/mol。此不飽和基當量為100g/mol以上的情況，對於進一步提高耐熱分解性、耐熱黃變性而言為有效果的。另一方面，此不飽和基當量未達4000g/mol的情況，對於 進一步提高感度而言為有效果的。 Further, in the case where the copolymer (A) has an unsaturated group, the unsaturated group equivalent thereof is not limited, and is usually from 100 to 4,000 g/mol, preferably from 200 to 3,000 g/mol. When the unsaturated group equivalent is 100 g/mol or more, it is effective for further improving thermal decomposition resistance and heat yellowing resistance. On the other hand, when the unsaturated base equivalent is less than 4000 g/mol, It is effective to further improve the sensitivity.

進一步而言，本發明關於一種樹脂組成物，其係含有共聚物(A)、溶劑(B)及任意地反應性稀釋劑(C)。另外，本發明之感光性樹脂組成物含有共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)及任意地著色劑(E)。 Further, the present invention relates to a resin composition comprising a copolymer (A), a solvent (B) and optionally a reactive diluent (C). Further, the photosensitive resin composition of the present invention contains the copolymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and optionally the colorant (E).

溶劑(B)只要是不與共聚物(A)發生反應的非活性溶劑，則不受到特別限定。 The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the copolymer (A).

溶劑(B)可採用與製造共聚物(A)時(共聚合反應)所使用的溶劑相同的物質，或可直接使用共聚合反應後所含有的溶劑，亦可再加入。另外，在加入其他成分時，該處所共存的物質亦可。溶劑(B)的具體例子可列舉丙二醇單甲醚、丙二醇單甲醚醋酸酯、二丙二醇單甲醚醋酸酯、醋酸乙酯、醋酸丁基、醋酸異丙基、丙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、乙二醇單甲醚、二乙二醇單甲醚、甲基乙基酮、甲基異丁基酮、環己酮、乙二醇單乙基醚醋酸酯、二乙二醇乙基醚醋酸酯等。該等可單獨或組合兩種以上使用。另外，該等之中，係以在製造共聚物(A)時(共聚合反應)所使用的丙二醇單甲醚、丙二醇單甲醚醋酸酯等的甘醇醚系溶劑為佳。 The solvent (B) may be the same as the solvent used in the production of the copolymer (A) (copolymerization), or the solvent contained after the copolymerization reaction may be used as it is, or may be added. In addition, when other ingredients are added, the substances coexisting in the space may also be used. Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, and dipropylene glycol. Methyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate , diethylene glycol ethyl ether acetate and the like. These may be used alone or in combination of two or more. Further, among these, a glycol ether solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate used in the production of the copolymer (A) (copolymerization reaction) is preferred.

關於本實施形態之樹脂組成物或感光性樹脂組成物中的溶劑(B)的摻合量，若將該組成物中之溶劑(B)除外的成分之總和定為100質量份，則一般而言為30~1000質量份，宜為50~800質量份，較佳為100~700質 量份。只要是此範圍的摻合量，即可成為具有適當黏度的樹脂組成物或感光性樹脂組成物。 When the total amount of the solvent (B) in the resin composition or the photosensitive resin composition of the present embodiment is 100 parts by mass, the total amount of the components other than the solvent (B) in the composition is generally 100 parts by mass. It is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, preferably 100 to 700 mass. Quantities. As long as it is a blending amount in this range, it can be a resin composition or a photosensitive resin composition having an appropriate viscosity.

反應性稀釋劑(C)並未受到特別限定，而可列舉例如苯乙烯、α-甲基苯乙烯、α-氯甲基苯乙烯、乙烯基甲苯、二乙烯基苯、酞酸二烯丙酯、二烯丙基苯膦酸酯等的芳香族乙烯基系單體類；醋酸乙烯基、己二酸乙烯基等的聚羧酸單體類；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸β-羥乙酯、(甲基)丙烯酸羥丙酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、參(羥乙基)異氰尿酸酯之三(甲基)丙烯酸酯等的(甲基)丙烯酸系單體；三烯丙基氰尿酸酯等。該等可單獨或組合兩種以上使用。 The reactive diluent (C) is not particularly limited, and examples thereof include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate. An aromatic vinyl monomer such as diallyl phenylphosphonate; a polycarboxylic acid monomer such as vinyl acetate or adipic acid vinyl; methyl (meth)acrylate or (methyl) Ethyl acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, cis (hydroxyethyl) isocyanurate tris (meth) acrylate, etc. Methyl) acrylic monomer; triallyl cyanurate or the like. These may be used alone or in combination of two or more.

關於本實施形態之樹脂組成物或感光性樹脂組成物中的反應性稀釋劑(C)的摻合量，若將該組成物中之溶劑(B)除外的成分之總和定為100質量份，則一般而言為10~90質量份，宜為20~80質量份，較佳為25~70質量份。只要是在此範圍的摻合量，即可成為具有適當黏度的樹脂組成物或感光性樹脂組成物，感光性樹脂組成物會具有適當的光硬化性。 In the resin composition of the present embodiment or the amount of the reactive diluent (C) in the photosensitive resin composition, the total amount of the components excluding the solvent (B) in the composition is 100 parts by mass. It is generally 10 to 90 parts by mass, preferably 20 to 80 parts by mass, preferably 25 to 70 parts by mass. As long as it is a blending amount within this range, it can be a resin composition or a photosensitive resin composition having an appropriate viscosity, and the photosensitive resin composition has appropriate photocurability.

光聚合起始劑(D)並未受到特別限定，而可列舉例 如安息香、安息香甲基醚、安息香乙基醚等的安息香與其烷基醚類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、4-(1-第三丁基二氧基-1-甲基乙基)苯乙酮等的苯乙酮類；2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等的蒽醌類；2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮等的噻噸酮類；苯乙酮二甲基縮酮、苄基二甲基縮酮等的縮酮類；二苯甲酮、4-(1-第三丁基二氧基-1-甲基乙基)二苯甲酮、3,3’,4,4’-肆(第三丁基二氧基羰基)二苯甲酮等的二苯甲酮類；2-甲基-1-[4-(甲基硫代)苯基]-2-嗎啉基-丙烷-1-酮；2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁酮-1；醯基膦氧化物類；及氧雜蒽酮類等。該等可單獨或組合兩種以上使用。 The photopolymerization initiator (D) is not particularly limited, and examples thereof include Benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichlorobenzene Acetones such as ketone and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; 2-methylindole, 2-pentylindole, 2-third Anthraquinones such as butyl hydrazine and 1-chloroindole; thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone a ketal such as acetophenone dimethyl ketal or benzyl dimethyl ketal; benzophenone, 4-(1-tert-butyldioxy-1-methylethyl) a benzophenone such as benzophenone or 3,3',4,4'-fluorene (t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methyl Thio)phenyl]-2-morpholinyl-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1; fluorenyl Phosphine oxides; and xanthones. These may be used alone or in combination of two or more.

本實施形態之感光性樹脂組成物中的光聚合起始劑(D)的摻合量，若將感光性樹脂組成物中之溶劑(B)除外的成分之總和定為100質量份，則一般而言為0.1~30質量份，宜為0.5~20質量份，較佳為1~15質量份。只要是此範圍的摻合量，即可成為具有適當的光硬化性的感光性樹脂組成物。 In the photosensitive resin composition of the present embodiment, the blending amount of the photopolymerization initiator (D) is generally 100 parts by mass, and the total amount of the components excluding the solvent (B) in the photosensitive resin composition is generally 100 parts by mass. It is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass. As long as it is a blending amount in this range, it can become a photosensitive resin composition which has suitable photocurability.

著色劑(E)只要可溶解或分散於溶劑(B)，則不受特別限定，可列舉例如染料或顏料等。 The colorant (E) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B), and examples thereof include a dye or a pigment.

特別是在以往的感光性樹脂組成物的情況，若使用染料，則可得到輝度高的著色圖型，而與使用顏料的情況相比，會有著色圖型的耐熱性變低的問題。相對於此，在本實施形態之感光性樹脂組成物的情況，即使使用染料仍可 得到耐熱性優異的著色圖型。 In particular, in the case of the conventional photosensitive resin composition, when a dye is used, a color pattern having a high luminance can be obtained, and the heat resistance of the coloring pattern is lowered as compared with the case of using a pigment. On the other hand, in the case of the photosensitive resin composition of the present embodiment, even if a dye is used, A coloring pattern excellent in heat resistance is obtained.

從對溶劑(B)或鹼顯像液的溶解性、與感光性樹脂組成物中的其他成分的交互作用、耐熱性等的觀點看來，染料係以使用具有羧酸等的酸性基的酸性染料、酸性染料與氮化合物之鹽、酸性染料之磺醯胺體等為佳。這種染料的例子可列舉acid alizarin violet N；acid black 1、2、24、48；acid blue 1、7、9、25、29、40、45、62、70、74、80、83、90、92、112、113、120、129、147；acid chrome violet K；acid Fuchsin；acid green 1、3、5、25、27、50；acid orange 6、7、8、10、12、50、51、52、56、63、74、95；acid red 1、4、8、14、17、18、26、27、29、31、34、35、37、42、44、50、51、52、57、69、73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274；acid violet 6B、7、9、17、19；acid yellow1、3、9、11、17、23、25、29、34、36、42、54、72、73、76、79、98、99、111、112、114、116；food yellow3及該等的衍生物等。該等之中，以偶氮系、呫噸系、蒽醌系或酞青素系的酸性染料為佳。該等可因應目標的畫素顏色單獨或組合兩種以上使用。 From the viewpoints of solubility in the solvent (B) or the alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, and the like, the dye is acidated using an acidic group having a carboxylic acid or the like. A dye, a salt of an acid dye and a nitrogen compound, a sulfonamide of an acid dye, or the like is preferred. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36 42, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow3 and such derivatives. Among these, an acid dye of an azo type, a xanthene type, an anthraquinone type or an anthraquinone type is preferable. These may be used alone or in combination of two or more kinds of pixel colors depending on the target.

顏料的例子可列舉C.I.色素黃色1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150 、153、154、166、173、194、214等的黃色顏料；C.I.色素橙色13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等的橙色顏料；C.I.色素紅色9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等的紅色顏料；C.I.色素藍色15、15：3、15：4、15：6、60等的藍色顏料；C.I.色素紫色1、19、23、29、32、36、38等的紫色顏料；C.I.色素綠色7、36、58等的綠色顏料；C.I.色素褐色23、25等的褐色顏料；C.I.色素黑色1、7、碳黑、鈦黑色、氧化鐵等的黑色顏料等。這些顏料可因應目標的畫素顏色單獨或組合兩種以上使用。 Examples of the pigment include CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150 Yellow pigments of 153, 154, 166, 173, 194, 214, etc.; CI pigments orange 13, 13, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. Orange pigment; CI pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Red pigments such as; blue pigments of CI pigment blue 15, 15:3, 15:4, 15:6, 60; etc.; purple pigments of CI pigment purple 1, 19, 23, 29, 32, 36, 38, etc. ; CI pigment green green pigments such as 7, 36, 58; brown pigments such as CI pigment brown 23, 25; black pigments such as CI pigment black 1, 7, carbon black, titanium black, iron oxide, and the like. These pigments can be used singly or in combination of two or more depending on the pixel color of the target.

此外，亦可因應目標的畫素顏色，將上述染料及顏料組合使用。 In addition, the above dyes and pigments can be used in combination according to the target color.

在本實施形態之感光性樹脂組成物之中，在摻合著色劑(E)的情況，關於其摻合量，若將感光性樹脂組成物中的溶劑(B)除外的成分的總和定為100質量份，則一般而言為5~80質量份，宜為5~70質量份，較佳為10~60質量份。 In the photosensitive resin composition of the present embodiment, when the coloring agent (E) is blended, the total amount of the components excluding the solvent (B) in the photosensitive resin composition is defined as the blending amount. 100 parts by mass is generally 5 to 80 parts by mass, preferably 5 to 70 parts by mass, preferably 10 to 60 parts by mass.

在使用顏料作為著色劑(E)的情況，從提升顏料的分散性的觀點看來，亦可將周知的分散劑摻合至感光性樹脂組成物。分散劑係使用經時分散安定性優異的高分子分散劑，故為適合。高分子分散劑的例子可列舉胺甲酸乙酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙二醇二酯系分散劑、去水山梨醇脂肪族酯系分 散劑、脂肪族變性酯系分散劑等。這種高分子分散劑亦可使用以EFKA(EFKA CHEMICALS BV(EFKA)公司製)、Disperbyk(Byk-Chemie公司製)、Disparlon(楠本化成股份有限公司製)、SOLSPERSE(Zeneca公司製)等的商品名市售的物品。 In the case where a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. The dispersant is suitable for use as a polymer dispersant excellent in dispersion stability over time. Examples of the polymer dispersant include an urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, and a sorbitan fat. Family ester Powder, aliphatic modified ester dispersant, and the like. As the polymer dispersant, a product such as EFKA (EFKA CHEMICALS BV (EFKA)), Disperbyk (Byk-Chemie), Disparlon (manufactured by Nanmoto Chemical Co., Ltd.), and SOLSPERS (manufactured by Zeneca) can be used. A commercially available item.

在本實施形態之感光性樹脂組成物中，分散劑的摻合量只要因應所使用的顏料等的種類適當地設定即可。 In the photosensitive resin composition of the present embodiment, the blending amount of the dispersing agent may be appropriately set depending on the type of the pigment or the like to be used.

本實施形態之感光性樹脂組成物含有著色劑(E)的情況，共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)、著色劑(E)的摻合量一般而言，若將感光性樹脂組成物中的溶劑(B)除外的成分的總和定為100質量份，則共聚物(A)為5~80質量份、溶劑(B)為30~1000質量份、反應性稀釋劑(C)為10~90質量份、光聚合起始劑(D)為0.1~30質量份、著色劑(E)為5~80質量份，宜為共聚物(A)為8~70質量份、溶劑(B)為50~800質量份、反應性稀釋劑(C)為20~80質量份、光聚合起始劑(D)為0.5~20質量份、著色劑(E)為5~70質量份，更佳為共聚物(A)為10~60質量份、溶劑(B)為100~700質量份、反應性稀釋劑(C)為25~70質量份、光聚合起始劑(D)為1~15質量份、著色劑(E)為10~60質量份。 When the photosensitive resin composition of the present embodiment contains the colorant (E), the copolymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and the colorant (E) In general, when the total of the components other than the solvent (B) in the photosensitive resin composition is 100 parts by mass, the copolymer (A) is 5 to 80 parts by mass, and the solvent (B) 30 to 1000 parts by mass, 10 to 90 parts by mass of the reactive diluent (C), 0.1 to 30 parts by mass of the photopolymerization initiator (D), and 5 to 80 parts by mass of the colorant (E), preferably The copolymer (A) is 8 to 70 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and the photopolymerization initiator (D) is 0.5 to 20 mass. The amount of the coloring agent (E) is 5 to 70 parts by mass, more preferably 10 to 60 parts by mass of the copolymer (A), 100 to 700 parts by mass of the solvent (B), and 25 to 5 parts of the reactive diluent (C). 70 parts by mass, the photopolymerization initiator (D) is 1 to 15 parts by mass, and the colorant (E) is 10 to 60 parts by mass.

本實施形態之感光性樹脂組成物即使是在不含著色劑(E)的情況，共聚物(A)、溶劑(B)、反應性稀釋劑(C)、光聚合起始劑(D)的摻合量也適合採用上述數 值。 In the case where the photosensitive resin composition of the present embodiment does not contain the colorant (E), the copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D) The amount of blending is also suitable for the above number value.

關於本實施形態之樹脂組成物中的共聚物(A)、溶劑(B)的摻合量，若將樹脂組成物中的溶劑(B)除外的成分的總和定為100質量份，則共聚物(A)為50~100質量份，溶劑(B)為30~1000質量份，宜為50~800質量份，較佳為100~700質量份。 The blending amount of the copolymer (A) and the solvent (B) in the resin composition of the present embodiment is 100 parts by mass of the total of the components other than the solvent (B) in the resin composition. (A) is 50 to 100 parts by mass, and the solvent (B) is 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, preferably 100 to 700 parts by mass.

在本實施形態之樹脂組成物含有反應性稀釋劑(C)的情況，關於共聚物(A)、溶劑(B)、反應性稀釋劑(C)的摻合量，若樹脂組成物中的溶劑(B)除外的成分的總和定為100質量份，則共聚物(A)為10~90質量份、溶劑(B)為30~1000質量份、反應性稀釋劑(C)為10~90質量份，宜為共聚物(A)為20~80質量份、溶劑(B)為50~800質量份、反應性稀釋劑(C)為20~80質量份，較佳為共聚物(A)為30~75質量份、溶劑(B)為100~700質量份、反應性稀釋劑(C)為25~70質量份。 In the case where the resin composition of the present embodiment contains the reactive diluent (C), the amount of the copolymer (A), the solvent (B), and the reactive diluent (C) is the solvent in the resin composition. (B) The total of the excluded components is 100 parts by mass, and the copolymer (A) is 10 to 90 parts by mass, the solvent (B) is 30 to 1000 parts by mass, and the reactive diluent (C) is 10 to 90 parts by mass. The copolymer (A) is preferably 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, and the reactive diluent (C) is 20 to 80 parts by mass, preferably the copolymer (A) is 30 to 75 parts by mass, solvent (B) is 100 to 700 parts by mass, and reactive diluent (C) is 25 to 70 parts by mass.

本實施形態之感光性樹脂組成物除了可摻合上述成分以外，為了賦予既定的特性，還可摻合周知的偶合劑、均勻劑、熱聚合禁止劑等的周知的添加劑。該等的添加劑的摻合量只要在不阻礙本發明之效果的範圍，則不受到特別限定。 In addition to the above-mentioned components, the photosensitive resin composition of the present embodiment may be blended with a well-known additive such as a known coupling agent, a homogenizer, or a thermal polymerization inhibitor to impart a predetermined characteristic. The blending amount of the additives is not particularly limited as long as it does not inhibit the effects of the present invention.

本實施形態之感光性樹脂組成物可藉由使用周知的混合裝置，混合上述成分而製造。 The photosensitive resin composition of the present embodiment can be produced by mixing the above components using a well-known mixing device.

此外，本實施形態之感光性樹脂組成物，還可預先調 製出含有共聚物(A)及溶劑(B)的樹脂組成物然後與反應性稀釋劑(C)、光聚合起始劑(D)及任意的著色劑(E)混合而製造。此外，該樹脂組成物除了可用在調製本實施形態之感光性樹脂組成物之外，還可使用於其他用途。 Further, the photosensitive resin composition of the present embodiment can be adjusted in advance The resin composition containing the copolymer (A) and the solvent (B) is produced and then mixed with a reactive diluent (C), a photopolymerization initiator (D), and an arbitrary coloring agent (E) to produce. Further, the resin composition can be used for other purposes in addition to the preparation of the photosensitive resin composition of the present embodiment.

如上述方式所得到的本實施形態之感光性樹脂組成物係具有鹼顯像性，因此藉由使用鹼水溶液，可進行顯像。特別是本實施形態之感光性樹脂組成物，其感度或顯像性優異，同時可賦予耐熱分解性及耐熱黃變性優異的著色圖型。因此，本實施形態之感光性樹脂組成物適合使用作為各種光阻，特別是適合使用作為用來製造裝在有機EL顯示器、液晶顯示裝置、固體拍攝元件的彩色濾光片所使用的光阻。另外，本實施形態之感光性樹脂組成物可賦予耐熱分解性及耐熱黃變性等的各式各樣的特性優異的硬化膜，因此亦可使用於各種鍍膜、黏著劑、印刷油墨用黏結劑等。 Since the photosensitive resin composition of the present embodiment obtained as described above has alkali developability, development can be carried out by using an aqueous alkali solution. In particular, the photosensitive resin composition of the present embodiment is excellent in sensitivity and developability, and can provide a coloring pattern excellent in thermal decomposition resistance and heat yellowing resistance. Therefore, the photosensitive resin composition of the present embodiment is suitably used as various photoresists, and is particularly preferably used as a photoresist used for manufacturing a color filter mounted on an organic EL display, a liquid crystal display device, or a solid-state imaging device. In addition, the photosensitive resin composition of the present embodiment can provide a cured film excellent in various properties such as heat-resistant decomposability and heat-resistant yellowing, and can be used in various coating films, adhesives, and binders for printing inks. .

接下來，使用本發明之感光性樹脂組成物所製成的彩色濾光片作說明。本發明的彩色濾光片係具有由上述感光性樹脂組成物所得到的著色圖型。 Next, a color filter made of the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a color pattern obtained from the above-mentioned photosensitive resin composition.

以下使用圖式對本發明其中一個實施形態之彩色濾光片作說明。 Hereinafter, a color filter of one embodiment of the present invention will be described using a drawing.

圖1係本實施之彩色濾光片之剖面圖。在圖1之中，彩色濾光片係由基板1；形成於基板1上的RGB的畫素2及形成於畫素2的交界的黑色矩陣3；及形成於畫素2及 黑色矩陣3上的保護膜4所構成。在此構成之中，除了畫素2及黑色矩陣3(著色圖型)是使用上述感光性樹脂組成物來形成，其他構成可採用周知者。此外，如圖1所示的彩色濾光片只是一個例子，而不受此構成所侷限。 Figure 1 is a cross-sectional view of a color filter of the present embodiment. In FIG. 1, a color filter is a substrate 1; RGB pixels 2 formed on the substrate 1 and a black matrix 3 formed at the boundary of the pixel 2; and formed in the pixel 2 and The protective film 4 on the black matrix 3 is composed of. In this configuration, the pixel 2 and the black matrix 3 (coloring pattern) are formed using the above-described photosensitive resin composition, and other configurations can be employed. Further, the color filter shown in Fig. 1 is only an example and is not limited by this configuration.

接下來針對本發明其中一個實施形態之彩色濾光片之製造方法作說明。 Next, a method of manufacturing a color filter according to one embodiment of the present invention will be described.

首先，在基材1上形成著色圖型。具體而言，在基材1上依序形成黑色矩陣3及畫素2。此處，基材1並未受到特別限定，而可使用玻璃基板、矽基板、聚碳酸酯基板、聚酯基板、聚醯胺基板、聚醯胺醯亞胺基板、聚醯亞胺基板、鋁基板、印刷電路板、陣列基板等。 First, a color pattern is formed on the substrate 1. Specifically, the black matrix 3 and the pixel 2 are sequentially formed on the substrate 1. Here, the substrate 1 is not particularly limited, and a glass substrate, a ruthenium substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, or an aluminum may be used. Substrate, printed circuit board, array substrate, and the like.

著色圖型可藉由光蝕刻法形成。具體而言，將上述感光性樹脂組成物塗佈於基板1上而形成塗佈膜之後，隔著既定圖型的光罩使塗佈膜曝光，使曝光部分光硬化。然後，以鹼水溶液使未曝光部分顯像之後，藉由烘烤可形成既定的圖型。 The coloring pattern can be formed by photolithography. Specifically, after the photosensitive resin composition is applied onto the substrate 1 to form a coating film, the coating film is exposed through a mask of a predetermined pattern, and the exposed portion is photocured. Then, after the unexposed portion is developed with an aqueous alkali solution, a predetermined pattern can be formed by baking.

感光性樹脂組成物之塗佈方法並未受到特別限定，而可使用絲網印刷法、輥式塗佈法、簾式塗佈法、噴霧塗佈法、旋轉塗佈法等。另外，感光性樹脂組成物之塗佈後，亦可因應必要藉由使用循環式烘箱、紅外線加熱器、熱板等的加熱手段進行加熱以使溶劑(B)揮發。加熱條件並未受到特別限定，只要因應所使用的感光性樹脂組成物的種類適當地設定即可。一般而言只要在50℃~120℃的溫度加熱30秒鐘~30分鐘即可。 The coating method of the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. Further, after the application of the photosensitive resin composition, it is also necessary to heat the solvent (B) by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited, and may be appropriately set depending on the type of the photosensitive resin composition to be used. Generally, it is only required to be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

曝光所使用的光源並未受到特別限定，而可使用低壓水銀燈、中壓水銀燈、高壓水銀燈、氙燈、金屬鹵素燈等。另外，曝光量亦並未受到特別限定，只要因應所使用的感光性樹脂組成物的種類適當地調整即可。 The light source used for the exposure is not particularly limited, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. In addition, the amount of exposure is not particularly limited, and may be appropriately adjusted depending on the type of the photosensitive resin composition to be used.

顯像所使用的鹼水溶液並未受到特別限定，而可使用碳酸鈉、碳酸鉀、碳酸鈣、氫氧化鈉、氫氧化鉀等的水溶液；乙胺、二乙胺、二甲基乙醇胺等的胺系化合物之水溶液；3-甲基-4-胺基-N,N-二乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-羥乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-甲烷磺醯胺乙基苯胺、3-甲基-4-胺基-N-乙基-N-β-甲氧基乙基苯胺及該等的硫酸鹽、鹽酸鹽或對甲苯磺酸鹽等的對苯二胺系化合物之水溶液等。該等之中宜為使用對苯二胺系化合物之水溶液。此外，在該等的水溶液中亦可因應必要添加消泡劑或界面活性劑。另外，宜在藉由上述鹼水溶液進行顯像之後，進行水洗並使其乾燥。 The aqueous alkali solution used for development is not particularly limited, and an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide; an amine such as ethylamine, diethylamine or dimethylethanolamine can be used. An aqueous solution of a compound; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline And an aqueous solution of a p-phenylenediamine compound such as a sulfate, a hydrochloride or a p-toluenesulfonate. Among these, an aqueous solution of a p-phenylenediamine compound is preferably used. Further, an antifoaming agent or a surfactant may be added in these aqueous solutions as necessary. Further, it is preferred to carry out development by the aqueous alkali solution, followed by washing with water and drying.

烘烤的條件並未受到特別限定，只要因應所使用的感光性樹脂組成物的種類進行加熱處理即可。一般而言，只要在130~250℃下加熱10~60分鐘即可。 The baking conditions are not particularly limited, and may be heat treated in accordance with the type of the photosensitive resin composition to be used. In general, it can be heated at 130~250 °C for 10~60 minutes.

藉由使用黑色矩陣3用的感光性樹脂組成物及畫素2用的感光性樹脂組成物依序重覆如上述般的塗佈、曝光、顯像及烘烤，可形成所希望的著色圖型。 By using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2, the coating, exposure, development, and baking as described above are sequentially repeated to form a desired color map. type.

此外，在上述內容中，說明了藉由光硬化進行的著色圖型之形成方法，而如果使用摻合硬化促進劑及周知的環氧樹脂的感光性樹脂組成物代替光聚合起始劑(D)，則 在藉由噴墨法進行塗佈之後，藉由加熱，亦可形成所希望的著色圖型。 Further, in the above description, a method of forming a color pattern by photo hardening is described, and if a photosensitive resin composition containing a blending hardening accelerator and a well-known epoxy resin is used instead of the photopolymerization initiator (D) ),then After coating by the inkjet method, a desired color pattern can also be formed by heating.

接下來，在著色圖型(畫素2及黑色矩陣3)上形成保護膜4。保護膜4並未受到特別限定，只要使用周知的物質形成即可。 Next, the protective film 4 is formed on the coloring pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited as long as it is formed using a known substance.

以這種方式所製造的彩色濾光片，係使用感度或顯像性優異同時賦予耐熱分解性及耐熱黃變性優異的著色圖型的感光性樹脂組成物來製造，因此具有耐熱分解性及耐熱分解性優異的著色圖型。 The color filter produced in this manner is produced by using a photosensitive resin composition which is excellent in sensitivity and developability and imparts a coloring pattern excellent in thermal decomposition resistance and heat yellowing resistance, and thus has heat decomposition resistance and heat resistance. A coloring pattern with excellent decomposability.

[實施例] [Examples]

以下參照實施例對本發明作詳細地說明，而本發明不受這些實施例限定。此外，在此實施例之中所提到的份及百分率，只要沒有特別註明，則全部為質量基準。另外，酸價意指依照JIS K 6901 5.3所測得的共聚物(A)的酸價，中和共聚物(A)1g中所含有的酸性成分所需要的氫氧化鉀的mg數。另外，分子量(Mw)意指使用凝膠滲透層析(GPC)，採用下述條件測得的標準聚苯乙烯換算重量平均分子量。 The invention is described in detail below with reference to the examples, but the invention is not limited thereto. In addition, the parts and percentages mentioned in this embodiment are all based on quality unless otherwise specified. Further, the acid value means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the copolymer (A) in accordance with the acid value of the copolymer (A) measured in JIS K 6901 5.3. Further, the molecular weight (Mw) means a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions.

管柱：Shodex(註冊商標)」LF-804+LF-804(昭和電工股份有限公司製) Pipe column: Shodex (registered trademark) LF-804+LF-804 (made by Showa Denko Co., Ltd.)

管柱溫度：40℃ Column temperature: 40 ° C

試樣：共聚物的0.2%四氫呋喃溶液 Sample: 0.2% tetrahydrofuran solution of copolymer

展開溶劑：四氫呋喃 Developing solvent: tetrahydrofuran

偵測器：示差折射計(Shodex RI-71S)(昭和電工股份有限公司製) Detector: Differential Refractometer (Shodex RI-71S) (made by Showa Denko Co., Ltd.)

流速：1mL/min Flow rate: 1mL/min

以下揭示本發明之共聚物(A)的製造例。 The production example of the copolymer (A) of the present invention is disclosed below.

<製造實施例1> <Manufacturing Example 1>

在具備攪拌裝置、滴液漏斗、冷凝管、溫度計及氣體導入管的燒瓶中，加入189.7g的丙二醇單甲醚醋酸酯及147.4g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由4.4g的甲基丙烯酸二環戊酯(a-1)及37.0g的甲基丙烯酸(a-3)所構成之單體混合物中添加0.9g的第三丁基過氧-2-乙基已酸酯(聚合起始劑)，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物(A)。 In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were added. Thereafter, the mixture was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. Next, 0.9 g of a third butylperoxy group was added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). 2-ethylhexanoate (polymerization initiator), and the obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer (A).

接下來，在此共聚物中加入94.9g的丙二醇單甲醚，而得到試樣No.1(固體成分酸價126mgKOH/g、重量平均分子量20000)。 Next, 94.9 g of propylene glycol monomethyl ether was added to the copolymer to obtain sample No. 1 (solid content acid value: 126 mgKOH/g, weight average molecular weight: 20,000).

<製造實施例2> <Manufacturing Example 2>

同樣地，在燒瓶中加入189.7g的丙二醇單甲醚醋酸酯及147.4g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由4.4g的甲基丙烯酸二環戊酯(a-1)及37.0g的甲基 丙烯酸(a-3)所構成之單體混合物中添加0.9g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 189.7 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, in 4.4 g of dicyclopentyl methacrylate (a-1) and 37.0 g of methyl To the monomer mixture composed of acrylic acid (a-3), 0.9 g of t-butylperoxy-2-ethylhexanoate was added, and the obtained product was dropped from the dropping funnel into the flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.6g的三苯膦(觸媒)及0.6g的氫醌(聚合禁止劑)，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of hydroquinone (polymerization inhibiting agent) were added, and the mixture was carried out at 120 ° C. The addition reaction was carried out for 6 hours to give a copolymer (A).

接下來，在此共聚物中加入116.2g的丙二醇單甲醚，而得到試樣No.2(固體成分酸價90mgKOH/g、重量平均分子量22000)。 Next, 116.2 g of propylene glycol monomethyl ether was added to the copolymer to obtain sample No. 2 (solid content acid value: 90 mgKOH/g, weight average molecular weight: 22,000).

<製造實施例3> <Manufacturing Example 3>

同樣地，在燒瓶中加入160.5g的丙二醇單甲醚醋酸酯及99.2g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由6.6g的甲基丙烯酸二環戊酯(a-1)及85.2g的甲基丙烯酸縮水甘油酯(a-3)所構成之單體混合物中添加5.3g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, after adding 160.5 g of propylene glycol monomethyl ether acetate and 99.2 g of ethoxylated o-phenylphenol acrylate (a-2) to the flask, the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 5.3 g of a third butyl group was added to a monomer mixture composed of 6.6 g of dicyclopentanyl methacrylate (a-1) and 85.2 g of glycidyl methacrylate (a-3). Peroxy-2-ethylhexanoate, and the obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入41.9g的丙烯酸、0.7g的三苯膦及0.7g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物。 Next, after replacing the inside of the flask with air, 41.9 g of acrylic acid, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce a copolymer.

接下來，在此共聚物中加入60.8g的四氫苯二甲酸酐，在115℃下進行加成反應1小時，使其產生共聚物(A)。 Next, 60.8 g of tetrahydrophthalic anhydride was added to the copolymer, and an addition reaction was carried out at 115 ° C for 1 hour to produce a copolymer (A).

接下來，在此共聚物(A)中，加入287.8g的丙二醇單甲醚，而得到試樣No.3(固體成分酸價75mgKOH/g、重量平均分子量21000)。 Next, 287.8 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain sample No. 3 (solid content acid value: 75 mgKOH/g, weight average molecular weight: 21,000).

<製造實施例4> <Manufacturing Example 4>

同樣地，在燒瓶中加入215.1g的丙二醇單甲醚醋酸酯及91.8g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)、41.7g的馬來酸酐(a-3)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由4.4g的甲基丙烯酸二環戊酯(a-1)及25.1g的乙烯基甲苯(a-3)所構成之單體混合物中添加13.0g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 215.1 g of propylene glycol monomethyl ether acetate, 91.8 g of ethoxylated o-phenylphenol acrylate (a-2), and 41.7 g of maleic anhydride (a-3) were added to the flask. The nitrogen was replaced while stirring, and the temperature was raised to 120 °C. Next, 13.0 g of a third butylperoxy group was added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 25.1 g of vinyltoluene (a-3). 2-ethylhexanoate, and the obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入40.6g的2-羥乙基丙烯酸酯、1.0g的三乙胺(觸媒)及1.0g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 40.6 g of 2-hydroxyethyl acrylate, 1.0 g of triethylamine (catalyst), and 1.0 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C. In an hour, it is allowed to produce a copolymer (A).

接下來，在此共聚物(A)中加入109.8g的丙二醇單甲醚，而得到試樣No.4(固體成分酸價110mgKOH/g、重量平均分子量5800)。 Next, 109.8 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain sample No. 4 (solid content acid value: 110 mgKOH/g, weight average molecular weight: 5,800).

<製造實施例5> <Manufacturing Example 5>

同樣地，在燒瓶中加入217.2g的丙二醇單甲醚醋酸酯及187.6g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由4.4g的甲基丙烯酸二環戊酯(a-1)及24.1g的甲基丙烯酸(a-3)所構成之單體混合物中添加1.1g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 217.2 g of propylene glycol monomethyl ether acetate and 187.6 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 1.1 g of a third butylperoxy group was added to a monomer mixture composed of 4.4 g of dicyclopentanyl methacrylate (a-1) and 24.1 g of methacrylic acid (a-3). 2-ethylhexanoate, and the obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.7g的三苯膦及0.7g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.7 g of triphenylphosphine, and 0.7 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer (A).

接下來，在此共聚物中加入129.9g的丙二醇單甲醚，而得到試樣No.5(固體成分酸價43mgKOH/g、重量平均分子量13900)。 Next, 129.9 g of propylene glycol monomethyl ether was added to the copolymer to obtain sample No. 5 (solid content acid value: 43 mgKOH/g, weight average molecular weight: 13900).

<製造實施例6> <Manufacturing Example 6>

同樣地，在燒瓶中加入170.1g的丙二醇單甲醚醋酸酯及53.6g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在由66.0g的甲基丙烯酸二環戊酯(a-1)及43.0g的甲基丙烯酸(a-3)所構成之單體混合物中添加0.8g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述 燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 170.1 g of propylene glycol monomethyl ether acetate and 53.6 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 0.8 g of a third butylperoxy group was added to a monomer mixture composed of 66.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). 2-ethylhexanoate, the resulting product was dropped from the dropping funnel into the foregoing In the flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.5g的三苯膦(觸媒)及0.5g的氫醌(聚合禁止劑)，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine (catalyst), and 0.5 g of hydroquinone (polymerization inhibitor) were added, and the mixture was carried out at 120 ° C. The addition reaction was carried out for 6 hours to give a copolymer (A).

接下來，在此共聚物(A)中加入96.3g的丙二醇單甲醚，而得到試樣No.6(固體成分酸價125mgKOH/g、重量平均分子量25600)。 Next, 96.3 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain sample No. 6 (solid content acid value: 125 mgKOH/g, weight average molecular weight: 25,600).

<製造實施例7> <Manufacturing Example 7>

同樣地，在燒瓶中加入187.2g的丙二醇單甲醚醋酸酯及1.9g的降莰烯(a-1’)、147.4g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在37.0g的甲基丙烯酸(a-3)中添加0.9g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, after adding 187.2 g of propylene glycol monomethyl ether acetate and 1.9 g of norbornene (a-1') and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) to the flask, Nitrogen replacement was carried out while stirring, and the temperature was raised to 120 °C. Next, 0.9 g of t-butylperoxy-2-ethylhexanoate was added to 37.0 g of methacrylic acid (a-3), and the obtained product was dropped from the dropping funnel into the flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.6g的三苯膦及0.6g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer (A).

接下來，在此共聚物(A)中加入114.9g的丙二醇單甲醚，而得到試樣No.7(固體成分酸價91mgKOH/g、重 量平均分子量21500)。 Next, 114.9 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain a sample No. 7 (solid content acid value: 91 mgKOH/g, weight The average molecular weight is 21500).

<製造實施例8> <Manufacturing Example 8>

同樣地，在燒瓶中加入189.8g的丙二醇單甲醚醋酸酯及147.4g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在4.4g的甲基丙烯酸異冰片酯(a-1)及37.0g的甲基丙烯酸(a-3)中添加0.9g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 189.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 0.9 g of t-butylperoxy-2-ethylhexanoate was added to 4.4 g of isobornyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). The obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.6g的三苯膦及0.6g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer (A).

接下來，在此共聚物(A)中加入116.2g的丙二醇單甲醚，而得到試樣No.8(固體成分酸價90mgKOH/g、重量平均分子量21800)。 Next, 116.2 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain sample No. 8 (solid content acid value: 90 mgKOH/g, weight average molecular weight: 2,1800).

<製造實施例9> <Manufacturing Example 9>

同樣地，在燒瓶中加入197.8g的丙二醇單甲醚醋酸酯及147.4g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在4.7g的甲基丙烯酸2-甲基-2-金剛烷酯(a-1)及37.0g的甲基丙烯酸(a-3)中添加0.9g的第三丁基過氧-2-乙基 已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 197.8 g of propylene glycol monomethyl ether acetate and 147.4 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 0.9 g of t-butylperoxy-2 was added to 4.7 g of 2-methyl-2-adamantyl methacrylate (a-1) and 37.0 g of methacrylic acid (a-3). -ethyl The acid ester was obtained, and the obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.6g的三苯膦及0.6g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物(A)。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer (A).

接下來，在此共聚物(A)中加入108.5g的丙二醇單甲醚，而得到試樣No.9(固體成分酸價90mgKOH/g、重量平均分子量22500)。 Next, 108.5 g of propylene glycol monomethyl ether was added to the copolymer (A) to obtain sample No. 9 (solid content acid value: 90 mgKOH/g, weight average molecular weight: 22,500).

以下揭示作為比較品的共聚物之製造例。 The production example of the copolymer as a comparative product is disclosed below.

<製造比較例1> <Manufacturing Comparative Example 1>

同樣地，在燒瓶中加入218.1g的丙二醇單甲醚醋酸酯及193.0g的乙氧基化鄰苯基苯酚丙烯酸酯(a-2)後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在24.1g的甲基丙烯酸(a-3)中添加0.9g的第三丁基過氧-2-乙基已酸酯，將所得之物由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 218.1 g of propylene glycol monomethyl ether acetate and 193.0 g of ethoxylated o-phenylphenol acrylate (a-2) were placed in a flask, and the mixture was stirred with nitrogen and heated to 120 ° C. . Next, 0.9 g of t-butylperoxy-2-ethylhexanoate was added to 24.1 g of methacrylic acid (a-3), and the obtained product was dropped from the dropping funnel into the flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.6g的三苯膦及0.6g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.6 g of triphenylphosphine, and 0.6 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer.

接下來，在此共聚物中加入130.4g的丙二醇單甲醚 ，而得到試樣No.10(固體成分酸價44mgKOH/g、重量平均分子量24800)。 Next, 130.4 g of propylene glycol monomethyl ether was added to the copolymer. Thus, sample No. 10 (solid content acid value: 44 mgKOH/g, weight average molecular weight: 24,800) was obtained.

<製造比較例2> <Manufacturing Comparative Example 2>

同樣地，在燒瓶中加入160.0g的丙二醇單甲醚醋酸酯後，進行氮氣置換同時攪拌，並使其昇溫至120℃。接下來，在110.0g的甲基丙烯酸二環戊酯(a-1)、43.0g的甲基丙烯酸(a-3)中添加0.8g的第三丁基過氧-2-乙基已酸酯，將所得之物，由滴液漏斗滴入前述燒瓶中。滴入結束後，在120℃下攪拌2小時進行共聚合反應，使其產生共聚物。 Similarly, 160.0 g of propylene glycol monomethyl ether acetate was added to the flask, and the mixture was stirred while stirring with nitrogen, and the temperature was raised to 120 °C. Next, 0.8 g of t-butylperoxy-2-ethyl perester was added to 110.0 g of dicyclopentanyl methacrylate (a-1) and 43.0 g of methacrylic acid (a-3). The obtained product was dropped from the dropping funnel into the aforementioned flask. After completion of the dropwise addition, the mixture was stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to produce a copolymer.

接下來，將前述燒瓶內置換成空氣之後，加入14.2g的甲基丙烯酸縮水甘油酯、0.5g的三苯膦及0.5g的氫醌，在120℃下進行加成反應6小時，使其產生共聚物。 Next, after replacing the inside of the flask with air, 14.2 g of glycidyl methacrylate, 0.5 g of triphenylphosphine, and 0.5 g of hydroquinone were added, and an addition reaction was carried out at 120 ° C for 6 hours to produce Copolymer.

接下來，在此共聚物中加入91.9g的丙二醇單甲醚，而得到試樣No.11(固體成分酸價132mgKOH/g、重量平均分子量26300)。 Next, 91.9 g of propylene glycol monomethyl ether was added to the copolymer to obtain sample No. 11 (solid content acid value: 132 mgKOH/g, weight average molecular weight: 26,300).

使用試樣No.1~11，調製出透明光阻、彩色光阻(顏料型)及彩色光阻(染料型)。 Sample Nos. 1 to 11 were used to prepare a transparent photoresist, a color resist (pigment type), and a color resist (dye type).

<透明光阻之調製> <Modulation of Transparent Photoresist>

相對於試樣No.1~11的固體成分100質量份而言添加季戊四醇四丙烯酸酯(反應性稀釋劑)30質量份、2,2-二甲氧基-2-苯基苯乙酮(光聚合起始劑)4質量份，而調 製出感光性樹脂組成物，使用此物調製出透明光阻(實施例1~9及比較例1、2)。 30 parts by mass of pentaerythritol tetraacrylate (reactive diluent) and 2,2-dimethoxy-2-phenylacetophenone (light) were added to 100 parts by mass of the solid content of Sample Nos. 1 to 11. Polymerization initiator) 4 parts by mass, and adjusted A photosensitive resin composition was produced, and a transparent photoresist (Examples 1 to 9 and Comparative Examples 1 and 2) was prepared using the composition.

<藉由透明光阻進行的圖型形成> <pattern formation by transparent photoresist>

將所調製的透明光阻旋轉塗佈在邊長5cm的方形玻璃基板(無鹼玻璃基板)上，使最終硬化塗膜的厚度成為2.5μm，然後，藉由在90℃下加熱3分鐘使溶劑揮發。接下來，使塗膜的整個表面曝光(曝光量50mJ/cm2)，使其光硬化後，進一步藉由在230℃下烘烤30分鐘而得到硬化塗膜。 The prepared transparent photoresist was spin-coated on a square glass substrate (alkali-free glass substrate) having a side length of 5 cm so that the thickness of the final cured coating film became 2.5 μm, and then the solvent was heated by heating at 90 ° C for 3 minutes. Volatile. Next, the entire surface of the coating film was exposed (exposure amount: 50 mJ/cm 2 ), and after photohardening, it was further baked at 230 ° C for 30 minutes to obtain a cured coating film.

<由透明光阻所形成的塗膜之評估> <Evaluation of Coating Film Formed by Transparent Photoresist>

針對由透明光阻所形成的塗膜，評估耐熱分解性、耐熱黃變性及透明性。 The heat-resistant decomposition property, heat-resistant yellowing property, and transparency were evaluated about the coating film formed by the transparent photoresist.

(1)耐熱分解性的評估 (1) Evaluation of thermal decomposition resistance

使用由成膜於玻璃基板上的塗膜所切成的樣品，藉由進行熱重量分析(TGA)作評估。在此分析中，求得此樣品與將樣品加熱至220℃並保持2小時的樣品兩者之間的重量變化率。此評估之基準如以下所述。 A sample cut from a coating film formed on a glass substrate was evaluated by thermogravimetric analysis (TGA). In this analysis, the rate of change in weight between this sample and the sample that heated the sample to 220 ° C for 2 hours was determined. The basis for this assessment is as follows.

○：未達-2.0% ○: Less than -2.0%

×：-2.0%以上 ×: -2.0% or more

(2)耐熱黃變性的評估 (2) Evaluation of heat-resistant yellowing

將成膜於玻璃基板上的塗膜放置於230℃的乾燥機中1小時，使用日本電色工業股份有限公司製色差計SE2000比較加熱處理前後塗膜的著色。其評估基準如以下所述。 The coating film formed on the glass substrate was placed in a dryer at 230 ° C for 1 hour, and the color of the coating film before and after the heat treatment was compared using a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. The evaluation criteria are as follows.

○：△E＊ab未達0.3 ○: △ E * ab less than 0.3

×：△E＊ab為0.3以上 ×: ΔE * ab is 0.3 or more

(3)透明性的評估 (3) Evaluation of transparency

將成膜於玻璃基板上的塗膜放置於230℃的乾燥機中1小時，使用島津製作所股份有限公司製分光光度計UV-1650PC作測定加熱處理前後的塗膜在400nm的光線透過率，藉由調查此透過率的變化率以進行評估。其評估基準如以下所述。 The coating film formed on the glass substrate was placed in a dryer at 230 ° C for 1 hour, and a spectrophotometer UV-1650PC manufactured by Shimadzu Corporation was used to measure the light transmittance of the coating film before and after the heat treatment at 400 nm. The rate of change in this transmission rate is investigated to assess. The evaluation criteria are as follows.

○：透過率之變化率未達1% ○: The rate of change of transmittance is less than 1%

×：透過率之變化率為1%以上 ×: The rate of change of transmittance is 1% or more

將上述耐熱分解性、耐熱黃變性、透明性的評估結果揭示於表1。 The evaluation results of the above heat decomposition resistance, heat yellow resistance, and transparency are shown in Table 1.

由表1的結果可知，實施例1~9的透明光阻可賦予耐熱分解性、耐熱黃變性、透明性全部皆優異的圖型，相對於此，比較例1、2之透明光阻會產生耐熱分解性、耐熱黃變性、透明性的任一者皆不足的圖型。 As is clear from the results of Table 1, the transparent resists of Examples 1 to 9 can provide a pattern excellent in heat decomposition resistance, heat yellow resistance, and transparency. On the other hand, the transparent photoresists of Comparative Examples 1 and 2 are produced. Any of the types of heat-resistant decomposition, heat-resistant yellowing, and transparency are insufficient.

<彩色光阻(顏料型)之調製> <Modulation of color photoresist (pigment type)>

在填充了直徑0.5mm的二氧化鋯珠180質量份的SUS容器中加入10.00質量份的C.I色素綠色36、33.75質量份的PGMEA(溶劑)及6.25質量份的分散劑(Byk-Chemie Japan股份有限公司製Disperbyk-161)，藉由以塗料混合機混合3小時使其分散而得到綠色顏料分散液。 10.00 parts by mass of CI pigment green 36, 33.75 parts by mass of PGMEA (solvent) and 6.25 parts by mass of dispersant (Byk-Chemie Japan limited stock) were added to a SUS container filled with 180 parts by mass of zirconia beads having a diameter of 0.5 mm. Disperbyk-161, manufactured by the company, was dispersed by a paint mixer for 3 hours to obtain a green pigment dispersion.

接下來，藉由將所調製出的綠色顏料分散液、試樣No.1~11及其他成分混合，而調製出感光性樹脂組成物 ，使用此物調製出彩色光阻(顏料型)(實施例10~18及比較例3~4)。 Next, the photosensitive green resin composition is prepared by mixing the prepared green pigment dispersion liquid, sample Nos. 1 to 11 and other components. Using this material, a color resist (pigment type) was prepared (Examples 10 to 18 and Comparative Examples 3 to 4).

將此彩色光阻(顏料型)的摻合成分及其摻合量揭示於表2。 The blending composition of this color resist (pigment type) and its blending amount are disclosed in Table 2.

<藉由彩色光阻(顏料型)進行的圖型形成> <Form formation by color resist (pigment type)>

將所調製的彩色光阻(顏料型)旋轉塗佈於邊長5cm的方形玻璃基板(無鹼玻璃基板)上，並使曝光後的厚度成為1.5μm，然後藉由在90℃下加熱3分鐘使溶劑揮發並使其乾燥。接下來，在距離塗佈膜100μm之處配置既定圖型的光罩，隔著此光罩，使塗佈膜曝光(曝光量150mJ/cm2)，而使曝光部分發生光硬化。接下來，藉由將含有0.1質量%的碳酸鈉的水溶液在23℃的溫度下以 0.3MPa的壓力進行噴霧，使未曝光部分溶解顯像之後，藉由在230℃下烘烤30分鐘而形成既定的圖型。 The prepared color resist (pigment type) was spin-coated on a square glass substrate (alkali-free glass substrate) having a side length of 5 cm, and the thickness after exposure was 1.5 μm, and then heated at 90 ° C for 3 minutes. The solvent is volatilized and allowed to dry. Next, a mask of a predetermined pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed (the exposure amount was 150 mJ/cm 2 ) through the mask, and the exposed portion was photocured. Next, an aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C at a pressure of 0.3 MPa to dissolve the unexposed portion, and then baked at 230 ° C for 30 minutes. The established pattern.

<彩色光阻(顏料型)及圖型之確認> <Confirmation of color resist (pigment type) and pattern>

對於彩色光阻(顏料型)及圖型確認鹼顯像性、感度、耐熱黃變性及耐溶劑性。 The alkali developability, sensitivity, heat yellowing resistance, and solvent resistance were confirmed for the color resist (pigment type) and the pattern.

(4)鹼顯像性的評估 (4) Evaluation of alkali imaging

鹼顯像性係藉由鹼顯像後的殘渣及顯像形態作確認。 鹼顯像後的殘渣係藉由使用日立HighTechnologies股份有限公司製電子顯微鏡S-3400觀察鹼顯像後的圖型而作確認。其評估基準如以下所述。 The alkali imaging property was confirmed by the residue and development morphology after alkali development. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi HighTechnologies Co., Ltd. The evaluation criteria are as follows.

○：無殘渣 ○: no residue

×：有殘渣 ×: There is residue

顯像形態係以目視評估藉由鹼顯像除去未曝光部分的形態。此處，在負型光阻的顯像步驟之中，未硬化的未曝光部分會藉由鹼顯像液而溶解且由基板上脫離，而就其顯像形態而言，主要為脫離的部分成為大的結塊而剝落的剝離型；以及徐緩溶解及擴散的溶解型。前者的剝離型的情況，結塊會成為異物而殘留在系統內而容易污染其他顏色的畫素，故為不佳，亦即，以後者的溶解型為佳。 The development morphology was visually evaluated by removing the morphology of the unexposed portion by alkali imaging. Here, in the developing step of the negative photoresist, the unhardened unexposed portion is dissolved by the alkali developing solution and detached from the substrate, and in terms of its developing form, mainly the detached portion A peeling type that becomes a large agglomerate and peels off; and a dissolved type that slowly dissolves and diffuses. In the case of the peeling type of the former, the agglomerates may become foreign matter and remain in the system, and may easily contaminate pixels of other colors, which is not preferable, that is, the latter is preferable.

○：溶解型 ○: dissolved type

×：剝離型 ×: peeling type

(5)感度的評估 (5) Assessment of sensitivity

實行上述使用噴霧的鹼顯像30秒鐘，所測得鹼顯像前後圖型厚度的減少量即為感度。此圖型厚度的減少量愈少，可說是感度愈為良好，因此其評估基準如以下所述。 The above-described alkali development using a spray was carried out for 30 seconds, and the amount of decrease in the thickness of the pattern before and after the alkali image was measured was the sensitivity. The less the thickness reduction of this pattern is, the better the sensitivity is, so the evaluation criteria are as follows.

○：未達0.20μm ○: less than 0.20 μm

×：0.20μm以上 ×: 0.20 μm or more

(6)耐熱黃變性的評估 (6) Evaluation of heat-resistant yellowing

耐熱黃變性除了不使用光罩而整面曝光使其硬化，最終塗膜的膜厚改變為2.5μm以外，係以與上述同樣的方式使其光硬化，將所形成的塗膜在230℃的乾燥機中放置1小時，使用日本電色工業股份有限公司製色差計SE2000對加熱處理前後塗膜的著色作比較。此評估的基準如以下所述。 The heat-resistant yellowing was hardened by the entire surface exposure without using a photomask, and the film thickness of the final coating film was changed to 2.5 μm, and the light was hardened in the same manner as above, and the formed coating film was at 230 ° C. The mixture was placed in a dryer for 1 hour, and the color of the coating film before and after the heat treatment was compared using a color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. The basis for this evaluation is as follows.

○：△E＊ab未達0.3 ○: △E * ab is less than 0.3

×：△E＊ab為0.3以上 ×: ΔE * ab is 0.3 or more

(7)耐溶劑性的評估 (7) Evaluation of solvent resistance

耐溶劑性係使用與耐熱黃變評估樣品同樣的方式製作的塗膜，在容量500mL的附蓋玻璃瓶中加入200mL的正甲基-2-吡咯烷酮，將圖型樣品浸漬於其中之後，在23℃下，使用島津製作所股份有限公司製分光光度計UV-1650PC測定1小時後的顏色變化。此評估基準如以下所述。 Solvent resistance was carried out by using a coating film prepared in the same manner as the heat-resistant yellowing evaluation sample, and 200 mL of n-methyl-2-pyrrolidone was placed in a 500 mL-capped glass vial, and the pattern sample was immersed therein, at 23 The color change after one hour was measured using a spectrophotometer UV-1650PC manufactured by Shimadzu Corporation. This evaluation benchmark is as follows.

○：△E＊ab未達0.3 ○: △E * ab is less than 0.3

×：△E＊ab為0.3以上 ×: △ E * ab of 0.3 or more

將上述鹼顯像性、感度、耐熱黃變性及耐溶劑性的評估結果揭示於表3。 The evaluation results of the above-mentioned alkali developability, sensitivity, heat yellowing resistance, and solvent resistance are shown in Table 3.

由表3的結果可知，實施例10~18的彩色光阻(顏料型)可賦予鹼顯像性及感度良好，耐熱黃變性及耐溶劑性優異的圖型，相對於此，比較例3~4的彩色光阻(顏料型)會產生鹼顯像性與感度不佳，耐熱黃變性或耐溶劑性不充分的圖型。 As is clear from the results of Table 3, the color resists (pigment type) of Examples 10 to 18 can provide a pattern having excellent alkali developability and sensitivity, and excellent heat yellowing resistance and solvent resistance, whereas Comparative Example 3 is used. The color resist (pigment type) of 4 produces a pattern of poor alkali developability and sensitivity, and insufficient heat yellowing or solvent resistance.

<彩色光阻(染料型)之調製> <Modulation of color photoresist (dye type)>

藉由將染料(acid green3)、試樣No.1~11及其他成分混合，而調製出感光性樹脂組成物，使用此組成物調製彩色光阻(染料型)(實施例19~27及比較例5~6) 。將此彩色光阻(染料型)的摻合成分及其摻合量揭示於表4。 A photosensitive resin composition was prepared by mixing an acid (acid green 3), sample Nos. 1 to 11 and other components, and a color resist (dye type) was prepared using the composition (Examples 19 to 27 and comparison) Example 5~6) . The blending composition of this color resist (dye type) and its blending amount are disclosed in Table 4.

<藉由彩色光阻(染料型)進行的圖型形成> <Form formation by color resist (dye type)>

除了使用彩色光阻(染料型)以外，係以與藉由彩色光阻(顏料型)進行的圖型形成同樣的方式形成既定的圖型。 In addition to the use of a color resist (dye type), a predetermined pattern is formed in the same manner as the pattern formation by a color resist (pigment type).

<彩色光阻(染料型)及圖型之評估> <Evaluation of color resist (dye type) and pattern>

使用與彩色光阻(顏料型)同樣的方法評估鹼顯像性、感度、耐熱黃變性及耐溶劑性。 The alkali developability, sensitivity, heat yellowing resistance, and solvent resistance were evaluated in the same manner as the color resist (pigment type).

將上述鹼顯像性、感度、耐熱黃變性及耐溶劑性的評估結果揭示於表5。 The evaluation results of the above-mentioned alkali developability, sensitivity, heat yellowing resistance, and solvent resistance are shown in Table 5.

由表5的結果可知，實施例19~27之彩色光阻(染料型)可賦予鹼顯像性及感度良好，耐溶劑性優異的圖型，相對於此，比較例5~6的彩色光阻(染料型)的鹼顯像性與感度不佳，會產生耐熱黃變性或耐溶劑性不充分的圖型。 As is clear from the results of Table 5, the color resists (dye type) of Examples 19 to 27 can provide a pattern having excellent alkali developability and sensitivity, and excellent solvent resistance, whereas the color light of Comparative Examples 5 to 6 is used. Resistance (dye type) has poor alkali developability and sensitivity, and produces a pattern of heat-resistant yellowing or insufficient solvent resistance.

由以上的結果可知，依據本發明可提供一種感光性樹脂組成物，其係感度或顯像性良好，同時可賦予耐熱分解性、耐熱黃變性及耐溶劑性優異的著色圖型。另外，依據本發明還可提供一種彩色濾光片，其係具有耐熱分解性及耐熱黃變性優異的著色圖型。 From the above results, according to the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity and developability, and which is capable of imparting a coloring pattern excellent in heat decomposition resistance, heat yellowing resistance, and solvent resistance. Further, according to the present invention, it is also possible to provide a color filter which has a coloring pattern excellent in heat decomposition resistance and heat yellow resistance.

1‧‧‧基板 1‧‧‧Substrate

2‧‧‧畫素 2‧‧‧ pixels

3‧‧‧黑色矩陣 3‧‧‧Black matrix

4‧‧‧保護膜 4‧‧‧Protective film

圖1係本發明其中一個實施形態的彩色濾光片之剖面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a color filter of one embodiment of the present invention.

Claims (12)

一種共聚物(A)，其係使具有碳數10~20之橋接環式烴基的聚合性單體(a-1)及/或下述化學式(1)所表示之聚合性單體(a-1’)與下述化學式(2)所表示之聚合性單體(a-2)聚合而成，且重量平均分子量(聚苯乙烯換算之重量平均分子量)為1000~50000，且含有羧基，酸價為20~300KOHmg/g， (式(1)中之X及Y各自獨立，表示氫原子、可為直鏈或分支之碳數1~4之烴基，R1及R2各自獨立，而為氫原子、羧基或可具有取代基之碳數1~20之烴基，亦可採取將R1及R2連結的環狀構造) (式(2)中之R3表示氫原子或甲基且n表示1~4之整數)。 A copolymer (A) which is a polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms and/or a polymerizable monomer represented by the following chemical formula (1) (a- 1') is polymerized with the polymerizable monomer (a-2) represented by the following chemical formula (2), and has a weight average molecular weight (weight average molecular weight in terms of polystyrene) of 1,000 to 50,000, and contains a carboxyl group and an acid. The price is 20~300KOHmg/g, (X and Y in the formula (1) are each independently and represent a hydrogen atom, a hydrocarbon group having a carbon number of 1 to 4 which may be a straight chain or a branched group, and R 1 and R 2 are each independently a hydrogen atom, a carboxyl group or may have a substitution. A hydrocarbon group having 1 to 20 carbon atoms may be a cyclic structure in which R 1 and R 2 are bonded) (R 3 in the formula (2) represents a hydrogen atom or a methyl group and n represents an integer of 1 to 4). 如申請專利範圍第1項之共聚物(A)，其中含有不飽和基。 The copolymer (A) of claim 1 which contains an unsaturated group. 如申請專利範圍第1項之共聚物(A)，其中前述 碳數10~20之具有橋接環式烴基之聚合性單體(a-1)係含有選自(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯之至少1種。 Copolymer (A) as claimed in claim 1 wherein the foregoing The polymerizable monomer (a-1) having a bridged cyclic hydrocarbon group having 10 to 20 carbon atoms is selected from the group consisting of dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (methyl). At least one of isobornyl acrylate and adamantyl (meth) acrylate. 如申請專利範圍第1項之共聚物(A)，其中進一步使具有乙烯性不飽和基的自由基聚合性單體(a-3)聚合而成。 The copolymer (A) according to the first aspect of the invention, wherein the radically polymerizable monomer (a-3) having an ethylenically unsaturated group is further polymerized. 如申請專利範圍第4項之共聚物(A)，其係以前述聚合性單體(a-1)及/或(a-1’)以莫耳比而計為2~50%，前述聚合性單體(a-2)為10~80%，前述聚合性單體(a-3)為18~88%的比例聚合。 The copolymer (A) according to claim 4, wherein the polymerizable monomer (a-1) and/or (a-1') is 2 to 50% in terms of a molar ratio, and the polymerization is carried out. The monomer (a-2) is 10 to 80%, and the polymerizable monomer (a-3) is polymerized in a ratio of 18 to 88%. 如申請專利範圍第4項之共聚物(A)，其中前述聚合性單體(a-3)係選自不飽和一元酸、不飽和多元酸酐、或(甲基)丙烯酸縮水甘油酯之1種或2種以上。 The copolymer (A) according to claim 4, wherein the polymerizable monomer (a-3) is one selected from the group consisting of an unsaturated monobasic acid, an unsaturated polybasic acid anhydride, or a glycidyl (meth)acrylate. Or two or more. 一種樹脂組成物，其係含有如申請專利範圍第1~6項中任一項之共聚物(A)及溶劑(B)。 A resin composition containing the copolymer (A) and the solvent (B) according to any one of claims 1 to 6. 如申請專利範圍第7項之樹脂組成物，其中進一步含有反應性稀釋劑(C)。 The resin composition of claim 7, which further contains a reactive diluent (C). 一種感光性樹脂組成物，其係含有如申請專利範圍第1~6項中任一項之共聚物(A)、溶劑(B)、反應性稀釋劑(C)及光聚合起始劑(D)。 A photosensitive resin composition containing the copolymer (A), the solvent (B), the reactive diluent (C), and a photopolymerization initiator (D) according to any one of claims 1 to 6. ). 如申請專利範圍第9項之感光性樹脂組成物，其中進一步含有由染料及/或顏料所構成之著色劑(E)。 The photosensitive resin composition of claim 9, which further comprises a coloring agent (E) composed of a dye and/or a pigment. 如申請專利範圍第10項之感光性樹脂組成物， 其係彩色濾光片用感光性樹脂組成物。 For example, the photosensitive resin composition of claim 10, This is a photosensitive resin composition for a color filter. 一種彩色濾光片，其係使含有如申請專利範圍第11項之感光性樹脂組成物的光阻塗膜硬化而成。 A color filter obtained by curing a photoresist coating film containing the photosensitive resin composition of claim 11 of the patent application.
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