TWI378321B - Thermosetting resin composition for producing color filter for cmos image sensor, color filter comprising transparent film formed using the compositon and cmos image sensor using the color filter - Google Patents
Thermosetting resin composition for producing color filter for cmos image sensor, color filter comprising transparent film formed using the compositon and cmos image sensor using the color filter Download PDFInfo
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- TWI378321B TWI378321B TW097106107A TW97106107A TWI378321B TW I378321 B TWI378321 B TW I378321B TW 097106107 A TW097106107 A TW 097106107A TW 97106107 A TW97106107 A TW 97106107A TW I378321 B TWI378321 B TW I378321B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
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Description
1378321 九、發明說明: 【發明所屬之技術領域:! 相關申請案之交互參照 本非臨時專利申請案依據35 USC條款119請求韓國專 5 利申請案第10-2007-0059842號,申請日2007年6月19日之優 先權,該案全文揭示以引用方式併入此處。 發明領域1378321 IX. Invention: [Technical field of invention:! Cross-reference of related application This non-provisional patent application is based on 35 USC clause 119 and requests for Korean patent application No. 10-2007-0059842, application date 2007 Priority is claimed on June 19, the entire disclosure of which is incorporated herein by reference. Field of invention
本發明係關於一種製造用於互補性金屬氧化物半導體 (CMOS)影像感應器之彩色濾光片的熱固性樹脂組成物,_ 10種包含使用該組成物所形成之透明薄膜的彩色濾光片,以 及一種使用該彩色濾光片的CMOS影像感應器。The present invention relates to a thermosetting resin composition for manufacturing a color filter for a complementary metal oxide semiconductor (CMOS) image sensor, 10 color filters including a transparent film formed using the composition, And a CMOS image sensor using the color filter.
t先前技術3 發明背景 景〉像感應器所使用的彩色據光片包括形成於該彩色渡 15光片表面下方及表面上方之一透明薄膜來改良平坦度與保 護該衫色濾光片。該透明薄臈於可見光區必須為光學透 明,具有高薄膜強度,且具有足夠耐熱性及耐化學性來忍 纽透明薄膜形成後之隨後處理諸如加熱、清潔、顯影及 侧。特定言之’用於影像感應器之彩色濾光片的底層透 20明薄膜必須為可遏止照射用來製作—彩色光阻之圖樣的紫 夕卜光的反射’因而防止由於各項不良因素諸如光暈和駐波 等造成彩色濾光片中之圖樣缺陷。 日本專利公開案平1-134306 ,昭62-163016及昭 63-1311〇3揭示彩色遽光片用之透明薄膜組成物,包含f基 5 丙歸竣縮水甘油酯、聚醯亞胺及蜜胺樹脂與環氧樹脂之混 &物作為主要組分。 環氧樹脂組成物可用來製造具有可靠的黏著強度、耐 熱性、耐化學性及防水性之彩色濾光片用之保護膜。例如, 曰本專利公開案平08-050289揭示一種包含甲基丙烯酸縮 水甘油酯聚合物及酚系硬化劑之可硬化樹脂组成物。此 外,日本專利公開案平〇8_2〇1617揭示一種透明薄膜用之樹 月曰’’且成物,包含環氧樹脂、硬化劑及有機溶劑,其中該硬 化劑為苯㈣·順讀二酐共聚物與胺之反應產物。 逋* %氧樹脂係恰在施用前與硬化劑混合(所謂之「二 P刀式組成物」),㈣在於環氧樹脂與硬化劑之反應快 速。已知環氧樹脂不適合用於製備一部分式組成物Μ曰二 部分式組祕之處理複雜且不適合祕玉業規模製備。 前述先前技術皆未曾揭示包含環氧樹脂之一部分式组 成物其可㈣滿足透日騎、薄_度、_性、魏性及BACKGROUND OF THE INVENTION The color light film used in the image sensor includes a transparent film formed below and above the surface of the color light film to improve flatness and protect the color filter. The transparent thin crucible must be optically transparent in the visible light region, have high film strength, and have sufficient heat resistance and chemical resistance to impart subsequent treatment such as heating, cleaning, development, and side after formation of the transparent film. Specifically, the underlying film of the color filter used for the image sensor must be a reflection of the violet light that can suppress the illumination used to make the pattern of the color photoresist, thus preventing various adverse factors such as Halo and standing waves cause defects in the pattern in the color filter. Japanese Patent Laid-Open Publication No. Hei 1-134306, No. Sho 62-163016, and No. Sho 63-1311 No. 3 disclose a transparent film composition for color calendering sheets, comprising f-based 5 glycerol glycosides, polyimine and melamine A mixture of resin and epoxy resin is used as a main component. The epoxy resin composition can be used to produce a protective film for a color filter having reliable adhesion strength, heat resistance, chemical resistance, and water repellency. For example, Japanese Laid-Open Patent Publication No. Hei 08-050289 discloses a hardenable resin composition comprising a glycidyl methacrylate polymer and a phenolic hardener. In addition, Japanese Patent Publication No. 8-2〇1617 discloses a tree of a transparent film, comprising an epoxy resin, a hardener and an organic solvent, wherein the hardener is a benzene (tetra)·cis dianhydride copolymer. The reaction product of the amine and the amine.逋*% oxygen resin is mixed with the hardener just before application (so-called "two-P blade composition"), and (d) is that the reaction between the epoxy resin and the hardener is fast. It is known that epoxy resins are not suitable for the preparation of a part of the composition. The treatment of the two-part group is complicated and is not suitable for the scale preparation of the secret jade industry. None of the foregoing prior art discloses that a partial composition comprising an epoxy resin can (4) satisfy the day-to-day riding, thinness, degree, and sexuality.
物生等要求。此外,未曾發展出可吸收紫外光之彩色遽 光片用之透明膜。 【明内J 發明概要 邳,提供—種製造彩色嘑来片之 熱固性樹脂組成物。本發明 ^慮先片之 Θ „ 固性樹脂組成物具有優異 的黏者強度、透明度、溥膜竑 ..^ ^ 、又、耐熱性、耐酸性、耐鹼 性及長麵存*疋数十錢特定 本發明之熱固性樹脂紐们系外先 成物包含有機溶劑及具有式 2、3及4表示之結構單元之自行硬化共聚物 R. A- ⑴ 其中Ri為氫原子或甲基及η為1至10之整數 R2Physical requirements and other requirements. Further, a transparent film for a color ray film which can absorb ultraviolet light has not been developed. [Mingna J Summary of Invention 邳, provides a thermosetting resin composition for producing colored enamel sheets. The invention has the advantages of the first film „ The solid resin composition has excellent adhesive strength, transparency, enamel film 竑.. ^ ^, heat resistance, acid resistance, alkali resistance and long surface storage * 疋 tens The thermosetting resin of the present invention is an external precursor comprising an organic solvent and a self-hardening copolymer having the structural unit represented by Formulas 2, 3 and 4, wherein R is a hydrogen atom or a methyl group and η is An integer R2 from 1 to 10
〇>-〇+c-t-〇H (2) 其中R2為氫原子或甲基及m為1至1〇之整數; R3’+民-〇>-〇+c-t-〇H (2) wherein R2 is a hydrogen atom or a methyl group and m is an integer from 1 to 1〇; R3’+民-
OH 〇 (3) 其中R3為氫原子或甲基;及 R4 -C- H2 ο )—ζ ⑷ 其中h為氫原子或甲基及Ζ為係選自於下列基團OH 〇 (3) wherein R 3 is a hydrogen atom or a methyl group; and R 4 -C- H 2 ο )-ζ (4) wherein h is a hydrogen atom or a methyl group and hydrazine is selected from the group consisting of the following groups
ΟΗΟΗ
及 (5)< 該自行硬化共聚物包括約5莫耳%至約9〇莫耳%式1結 構單元,約1莫耳%至約30莫耳%式2結構單元,^莫耳二 至約30莫耳%式3結構單元,及級5莫耳%至約2〇莫耳 1378321And (5) < the self-hardening copolymer comprises from about 5 mol% to about 9 mol% of the structural unit of formula 1, about 1 mol% to about 30 mol% of the structural unit of formula 2, ^Mo Er II to About 30 moles of formula 3 structural units, and grades of 5 moles to about 2 inches of mull 1383721
結構單元" 自行硬化共聚物進一步包括式6結構單元: 〇久广。The structural unit " self-hardening copolymer further comprises the structural unit of formula 6: 〇久广.
X (6) 其中X係選自%如、β及(^_Υ,〇為⑻之整數, ρ為4至12之整數,及γ係選自氫原子、CiQ低碳烧基及 C1-C4低碳院氧基。 式6結構單元係以約〇5莫耳%至約2〇莫耳%之數量存 量。 自行硬化共聚物具有由約1,000至約1〇〇〇 〇〇〇之範圍 10 之重量平均分子量。 本發明之熱固性樹脂組成物進一步包含環氧化合物。 本發明之熱固性樹脂組成物包含約1 %至約Μ%重量比 自行硬化共聚物,約1%至約45%重量比環氧化合物,及差 額為有機溶劑。X (6) wherein X is selected from the group consisting of %, β and (^_Υ, 〇 is an integer of (8), ρ is an integer from 4 to 12, and γ is selected from a hydrogen atom, a CiQ low carbon alkyl group and a C1-C4 low. Carbon-based oxygen. The structural unit of formula 6 is present in an amount of from about 5 mole percent to about 2 mole percent. The self-hardening copolymer has a weight ranging from about 1,000 to about 1 Torr. The thermosetting resin composition of the present invention further comprises an epoxy compound. The thermosetting resin composition of the present invention comprises from about 1% to about 5% by weight of a self-hardening copolymer, and from about 1% to about 45% by weight of an epoxy compound. , and the difference is an organic solvent.
15 該環氧化合物係選自於由雙酚A型環氧化合物、雙盼F 型環氧化合物、酚酚醛清漆樹脂型環氧化合物、甲酚酚醛 清漆樹脂型環氧化合物、及經取代之環氧化合物所組成之 組群。此等環氧化合物可單獨使用或呈其混合物使用。 自行硬化共聚物進一步包括選自於由下列所組成之組 20 群中之至少一個結構單元:(甲基)丙烯酸酯類包括(甲基)丙 烯酸甲酯、(甲基)丙烯酸乙酯、(曱基)丙烯酸丙酯、(甲基) 8 137832115 The epoxy compound is selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac resin type epoxy compound, a cresol novolac resin type epoxy compound, and a substituted ring. a group consisting of oxygen compounds. These epoxy compounds may be used singly or in a mixture thereof. The self-hardening copolymer further includes at least one structural unit selected from the group consisting of: (meth) acrylates including methyl (meth) acrylate, ethyl (meth) acrylate, (曱) Base) propyl acrylate, (methyl) 8 1378321
丙烯酸異丙酯、(曱基)丙烯酸丁酯、及(甲基)丙烯酸苄酯; 丙烯醯胺類包括N-曱基丙烯醯胺、N-乙基丙烯醯胺、N-異 丙基丙烯醯胺、N-羥甲基丙烯醯胺、N-曱基曱基丙烯醯胺、 N-乙基曱基丙烯醯胺、N-異丙基曱基丙烯醯胺、N-羥甲基 5 甲基丙烯醯胺、Ν,Ν-二甲基丙烯醯胺、N,N-二乙基丙烯醯 胺、Ν,Ν-二甲基甲基丙烯醯胺、及N,N-二乙基曱基丙烯醯 胺;苯乙烯類包括苯乙烯、α-甲基苯乙烯及羥基苯乙烯; Ν-乙烯基吡咯啶酮;Ν-乙烯基甲醯胺;Ν-乙烯基醯胺;及 Ν-乙稀基咪。坐。 10 本發明組成物進一步包含選自於聚(曱基)丙烯酸酯、尼 龍、聚酯、聚醯亞胺及聚矽中之至少一種聚合物。以100份 重量比自行硬化共聚物為基準,該聚合物係以約50份重量 比或以下之數量承載。 根據本發明之另一面相,提供一種包含使用該組成物 15 所形成之一透明膜之彩色濾光片。 根據本發明之又另一面相,提供一種使用該彩色濾光 片之影像感應器。 圖式簡單說明 第1圖為示意圖顯示CMOS影像感應器之結構。 20 第2圖為示意圖顯示藉光反射出現圖樣缺陷之機轉。 第3圖顯示經由將一 CMOS影像感應器用之一彩色光 阻施用至比較例1所形成之一透明膜,將該彩色光阻曝光及 顯影曝光後之彩色光阻所得之一圖樣形狀。 第4圖顯示經由將一 CMOS影像感應器用之一彩色光 9 1378321 阻施用至實例1所形成之一透明膜,將該彩色光阻曝光及顯 影曝光後之彩色光阻所得之一圖樣形狀。 I:實施方式3 較佳實施例之詳細說明 5 現在將於後文發明之詳細說明更完整說明本發明,其 中說明部分但非全部本發明之實施例。確實,本發明可以 多種不同形式具體實施,絕非囿限於此處所述之該等實施 例;反而此等實施例係用來讓本揭示可符合適用之法定要Isopropyl acrylate, butyl (meth) acrylate, and benzyl (meth) acrylate; acryl amides include N-mercapto acrylamide, N-ethyl acrylamide, N-isopropyl propylene hydride Amine, N-methylol acrylamide, N-fluorenyl decyl acrylamide, N-ethyl decyl acrylamide, N-isopropyl decyl acrylamide, N-methylol 5 methyl Acrylamide, hydrazine, hydrazine-dimethyl methacrylate, N,N-diethyl acrylamide, hydrazine, hydrazine-dimethyl methacrylamide, and N,N-diethyl decyl propylene Hydrazine; styrene includes styrene, α-methylstyrene and hydroxystyrene; Ν-vinylpyrrolidone; Ν-vinylformamide; Ν-vinyl decylamine; and Ν-ethylene mum. sit. The composition of the present invention further comprises at least one polymer selected from the group consisting of poly(indenyl)acrylate, nylon, polyester, polyimine, and polyfluorene. The polymer is supported in an amount of about 50 parts by weight or less based on 100 parts by weight of the self-hardening copolymer. According to another aspect of the present invention, there is provided a color filter comprising a transparent film formed using the composition 15. According to still another aspect of the present invention, an image sensor using the color filter is provided. Brief Description of the Drawings Figure 1 is a schematic diagram showing the structure of a CMOS image sensor. 20 Figure 2 is a schematic diagram showing the machine rotation of pattern defects caused by light reflection. Fig. 3 shows a pattern shape obtained by applying a color refractory film of a CMOS image sensor to a transparent film formed in Comparative Example 1, and exposing and developing the color resist of the color resist. Fig. 4 shows a pattern shape obtained by applying a CMOS image sensor with a color light 9 1378321 to a transparent film formed in Example 1, and exposing and developing the colored photoresist after exposure of the color resist. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION The present invention will now be described more fully hereinafter with reference to the appended claims, Indeed, the present invention may be embodied in a variety of different forms and is not limited to the embodiments described herein; rather, these embodiments are intended to enable the present disclosure to comply with applicable statutory
10 本發明提供一種熱固性樹脂組成物,其可用於製造 C Μ Ο S影像感應器用之彩色濾光片。特定言之,本發明之熱 固性樹脂組成物包含有機溶劑及具有紫外光(UV)吸收基團 之自行硬化共聚物。 該自行硬化共聚物具有式卜2、3及4表示之結構單元: 15 本發明之熱固性樹脂組成物包含有機溶劑及具有式 1、2、3及4表示之結構單元之自行硬化共聚物:10 The present invention provides a thermosetting resin composition which can be used for manufacturing a color filter for a C Μ S image sensor. Specifically, the thermosetting resin composition of the present invention contains an organic solvent and a self-hardening copolymer having an ultraviolet (UV) absorbing group. The self-hardening copolymer has the structural unit represented by the formulas 2, 3 and 4: 15 The thermosetting resin composition of the present invention comprises an organic solvent and a self-hardening copolymer having the structural unit represented by the formulas 1, 2, 3 and 4:
Ri +· 〇i-〇+C2-t^〇 ⑴ 其中艮為氩原子或甲基及η為1至10之整數;Ri +· 〇i-〇+C2-t^〇 (1) wherein 艮 is an argon atom or a methyl group and η is an integer from 1 to 10;
20 其中R2為氫原子或甲基及m為1至10之整數; 10 1378321 r320 wherein R 2 is a hydrogen atom or a methyl group and m is an integer from 1 to 10; 10 1378321 r3
OH ο (3) 其中R3為氫原子或曱基;及 R4OH ο (3) wherein R 3 is a hydrogen atom or a fluorenyl group; and R 4
/-0-2 〇/-0-2 〇
其中R4為氫原子或曱基及z為係選自於下列基團:Wherein R 4 is a hydrogen atom or a fluorenyl group and z is selected from the group consisting of the following groups:
由於式1結構單元可與式2、3及4結構單元加熱交聯, 故自行硬化共聚物具有熱固性質。具有式1至式4結構單元 之自行硬化共聚物可屬於任一型共聚物諸如隨機共聚物、 10 交替共聚物、嵌段共聚物或接枝共聚物。Since the structural unit of Formula 1 can be thermally crosslinked with the structural units of Formulas 2, 3 and 4, the self-hardening copolymer has thermosetting properties. The self-hardening copolymer having the structural unit of Formula 1 to Formula 4 may belong to any type of copolymer such as a random copolymer, a 10 alternating copolymer, a block copolymer or a graft copolymer.
該自行硬化共聚物包括約5莫耳°/〇至約90莫耳%式1結 構單元,約1莫耳%至約30莫耳%式2結構單元,約1莫耳% 至約30莫耳%式3結構單元,及約0.5莫耳%至約20莫耳%式4 結構單元。 15 特定言之,式4結構單元具有紫外光吸收基團(Z)。基 團(Z)的存在可防止由於各種不良因素導致圖樣缺陷的發 生。舉個實例,參照第2圖舉例說明之機轉,當彩色光阻曝 光時,彩色光阻之未曝光部分並未由來自於下方基材之紫 11 1378321 外光再度反射而硬化。 自行硬化共聚物進一步包括式6結構單元’其存在可改 良組成物之儲存安定性及薄膜硬度:The self-hardening copolymer comprises from about 5 moles per mole to about 90 mole percent of the structural unit of formula 1, from about 1 mole percent to about 30 mole percent of the structural unit of formula 2, from about 1 mole percent to about 30 moles. % structural unit of formula 3, and from about 0.5 mole % to about 20 mole % of structural unit of formula 4 . 15 Specifically, the structural unit of Formula 4 has an ultraviolet light absorbing group (Z). The presence of the group (Z) prevents the occurrence of pattern defects due to various adverse factors. For example, referring to the machine illustrated in Figure 2, when the color resist is exposed, the unexposed portion of the color resist is not hardened by the external reflection from the underlying substrate of the violet 11 1378321. The self-hardening copolymer further comprises a structural unit of formula 6 which has improved storage stability and film hardness of the composition:
(6)(6)
其中X係選自Η 及ό—Υ,〇為1至4之整數, Ρ為4至12之整數,及γ係選自氫原子、Cl-C4低碳烷基及 Ci-C4低碳炫氧基。Wherein X is selected from the group consisting of Η and ό-Υ, 〇 is an integer from 1 to 4, Ρ is an integer from 4 to 12, and γ is selected from the group consisting of a hydrogen atom, a Cl-C4 lower alkyl group, and a Ci-C4 low carbon oxyhydrogen. base.
式6結構單元係以約0.5莫耳%至約2 0莫耳%之數量存 量。 10 自行硬化共聚物之重量平均分子量為約1,000至約 1,000,000。當自行硬化共聚物具有重量平均分子量小於約 1,〇〇〇時’該自行硬化共聚物無法充分硬化。同時,當自行 硬化共聚物具有重量平均分子量大於約1,〇〇〇,〇〇〇時,共聚 物之溶解度減低或可能難以將該組成物施用至基材。以組 15 成物之總重為基準,自行硬化共聚物可以約1〇/〇至約45%重 量比之數量存在於該熱固性樹脂組成物。 本發明組成物中所使用之有機溶劑之種類並無特殊限 制。本發明有用之有機溶劑之實例包括但非限於:乙二醇 類包括乙二醇及二乙二醇;二醇醚類包括乙二醇一甲醚、 20 二乙二醇一曱醚、乙二醇二乙醚及二乙二醇二曱醚;二醇 醚乙酸酯類包括乙二醇一乙醚乙酸酯、二乙二醇一乙喊乙 12 1378321The structural unit of formula 6 is stored in an amount of from about 0.5 mole % to about 20 mole %. The self-hardening copolymer has a weight average molecular weight of from about 1,000 to about 1,000,000. When the self-hardening copolymer has a weight average molecular weight of less than about 1, ’, the self-hardening copolymer cannot be sufficiently hardened. Also, when the self-hardening copolymer has a weight average molecular weight greater than about 1, 〇〇〇, 〇〇〇, the solubility of the copolymer is reduced or it may be difficult to apply the composition to the substrate. The self-hardening copolymer may be present in the thermosetting resin composition in an amount of from about 1 Torr to about 45% by weight based on the total weight of the group. The kind of the organic solvent used in the composition of the present invention is not particularly limited. Examples of organic solvents useful in the present invention include, but are not limited to, ethylene glycols including ethylene glycol and diethylene glycol; glycol ethers including ethylene glycol monomethyl ether, 20 diethylene glycol monoterpene ether, and ethylene glycol. Alcohol diethyl ether and diethylene glycol dioxime ether; glycol ether acetates including ethylene glycol monoethyl ether acetate, diethylene glycol-ethyl shunting B 12 1378321
酸酯、及二乙二醇一丁醚乙酸酯;丙二醇類;丙二醇醚類 包括丙二醇一甲驗、丙二醇一乙謎、丙二醇一丙謎、丙二 醇一丁醚、丙二醇二甲醚、二丙二醇二甲醚、丙二醇二乙 醚、及二丙二醇二乙醚;丙二醇醚乙酸酯類包括丙二醇一 5 甲醚乙酸酯及二丙二醇一乙醚乙酸酯;醯胺類包括N-甲基 吡咯啶酮、二曱基曱醯胺及二甲基乙醯胺;酮類諸如異丁 酮(MEK)、甲基異丁基甲酮(MIBK)、及環己酮;石油溶劑 包括曱苯、二甲苯、及溶劑石腦油;酯類包括乙酸乙酯、 乙酸丁酯、及乳酸乙酯及其混合物。 10 除了含有自行硬化共聚物及其它組分外,有機溶劑可 組成組成物之其餘重量百分比。以組成物總重為基準,本 發明組成物包含有機溶劑之含量為約30%至約99%重量 比,例如約70%至約98%重量比。若組成物包括少於約30% 重量比有機溶劑,則難以將組成物施用至基材。同時,若 15 組成物包括超過約99%重量比有機溶劑,則難以形成夠厚 的保護膜。 為了改良耐蝕刻性及耐鹼性及調整流動性,該組成物 視需要可進一步包含環氧化合物。該環氧化合物可為選自 於由雙酚A型環氧化合物、雙酚F型環氧化合物、酚酚醛清 20 漆樹脂型環氧化合物、甲酚酚醛清漆樹脂型環氧化合物、 及經取代之環氧化合物等所組成之組群之環氧化合物。此 等環氧化合物可單獨使用或呈其混合物使用。該環氧化合 物具有於約50至約10,000範圍之重量平均分子量。以樹脂 組成物之總重為基準,該熱固性樹脂組成物中之環氧化合 13 1378321 ίο 15Acid esters, and diethylene glycol monobutyl ether acetate; propylene glycols; propylene glycol ethers including propylene glycol-method, propylene glycol-a-mystery, propylene glycol-propanol, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol Methyl ether, propylene glycol diethyl ether, and dipropylene glycol diethyl ether; propylene glycol ether acetates include propylene glycol 5-methyl ether acetate and dipropylene glycol monoethyl ether acetate; guanamines include N-methylpyrrolidone, diterpenes Ketones and dimethylacetamide; ketones such as isobutyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; petroleum solvents including toluene, xylene, and solvent naphtha The esters include ethyl acetate, butyl acetate, and ethyl lactate and mixtures thereof. 10 In addition to containing the self-hardening copolymer and other components, the organic solvent can constitute the remaining weight percent of the composition. The composition of the present invention comprises an organic solvent in an amount of from about 30% to about 99% by weight, such as from about 70% to about 98% by weight, based on the total weight of the composition. If the composition includes less than about 30% by weight of an organic solvent, it is difficult to apply the composition to the substrate. Meanwhile, if the composition of 15 contains more than about 99% by weight of an organic solvent, it is difficult to form a thick protective film. In order to improve etching resistance and alkali resistance and to adjust fluidity, the composition may further contain an epoxy compound as needed. The epoxy compound may be selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac 20 lacquer type epoxy compound, a cresol novolac resin type epoxy compound, and a substituted An epoxy compound of a group consisting of an epoxy compound or the like. These epoxy compounds may be used singly or in a mixture thereof. The epoxide has a weight average molecular weight in the range of from about 50 to about 10,000. The epoxidized composition in the thermosetting resin composition based on the total weight of the resin composition 13 1378321 ίο 15
20 物含量係於約1 %至約45%重量比,例如約5%至約30%重量 比之範圍。當環氧化合物之存在量低於約1%重量比時,可 月b導致使用該組成物所形成之透明薄膜之維度穩定性低 劣。同時,當環氧化合物之存在量大於約45%重量比時, 造成難以將該組成物施用至基材。 為了改良.·且成物性貝或對組成物賦與其它性質諸如 施用容易、薄膜硬度及對上方薄膜及下方薄膜之親和力, X自仃硬化八聚物視的要可包括選自於由下列所組成之組 群中之至少一個重複單元 (曱基)丙稀酸醋類包括(曱基)丙 烯酸甲酯、(甲基)丙烯酸 “、(甲基)丙稀酸丙醋、(甲基) 丙烯酸異丙酯 '(甲基)丙烯 ;碲醪丁酯、及(曱基)丙烯酸苄酯; 丙烯醯胺類包括N-甲基丙铋姑 β π歸蟪胺、Ν-乙基丙烯醯胺、Ν-異 丙基丙稀醯胺、:Ν-經甲某呙以 土内烯醯胺、Ν-甲基甲基丙烯醯胺、 Ν-乙基曱基丙烯醯胺、 秀丙基甲基丙烯醯胺、Ν-羥甲基 甲基丙烯醯胺、Ν,Ν-二甲a τ丞丙烯醯胺、N,N-二乙基丙烯醯 胺^•二甲基甲基丙烯_、及Ν,Ν·二乙基甲基丙稀醯 胺,笨乙烯類包括苯乙炼、 \T,甲基苯乙烯及羥基苯乙烯; Μ-乙烯基吡咯啶酮;Ν χτ 崎基甲醯胺;Ν-乙烯基醯胺;及 Ν-乙烯基咪唑;等及其混合物 自行硬化共聚物可使化藝界已知之任—種適當方法 合成。至於非限制性實例, 遠自行硬化共聚物可使用自由 基聚合起始劑於本發明 加人Λ、 ·'、、固性樹脂組成物之相同有機溶 劑合成。 用於合成具有紫外光 久收基團之自行硬化共聚物之有 14 1378321The content of the compound is in the range of from about 1% to about 45% by weight, such as from about 5% to about 30% by weight. When the epoxy compound is present in an amount of less than about 1% by weight, the monthly b may cause the dimensional stability of the transparent film formed using the composition to be inferior. Meanwhile, when the epoxy compound is present in an amount of more than about 45% by weight, it is difficult to apply the composition to the substrate. In order to improve the properties and impart other properties to the composition such as ease of application, film hardness and affinity for the upper film and the underlying film, the X self-hardening octamer may be selected from the following At least one repeating unit (mercapto) acrylic acid vinegar of the group consisting of (mercapto)methyl acrylate, (meth)acrylic acid, (meth)acrylic acid propylene vinegar, (meth)acrylic acid Isopropyl ester '(meth) propylene; butyl acrylate, and benzyl (meth) acrylate; propylene oxime amines include N-methyl propyl sulfoxide, Ν-ethyl acrylamide, Ν-isopropyl acrylamide, Ν-A 呙 醯 土 醯 醯 醯 醯 醯 醯 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 、 、 、 、 Indoleamine, hydrazine-hydroxymethylmethacrylamide, hydrazine, hydrazine-dimethyl oxahydrazine, N,N-diethyl acrylamide, dimethyl methacrylate, and hydrazine, Ν·Diethylmethyl propyl amide, stupid ethylene including phenyl acetonitrile, \T, methyl styrene and hydroxystyrene; Μ-vinyl pyrrolidone; Ν χ 基Amines; fluorene-vinyl decylamine; and hydrazine-vinylimidazole; and mixtures thereof self-hardening copolymers can be synthesized by any suitable method known in the art. For non-limiting examples, far self-hardening copolymers can be used. The free radical polymerization initiator is used in the synthesis of the same organic solvent of the composition of the present invention, and the solid resin composition. The self-hardening copolymer for synthesizing the ultraviolet light-receiving group has 14 1378321
機溶劑並無特殊限制而可與本發明之熱固性樹脂組成物使 用之有機溶劑相同。另一方面,聚合中之有機溶劑用量係 控制為,以該自行硬化共聚物於有機溶劑之溶液之重量為 基準,該自行硬化共聚物係以約3%至約50%重量比,例如 約5%至約30%重量比之數量存在。當該自行硬化共聚物於 溶液之濃度係低於約3%重量比時,聚合速率低,如此若干 單體維持未反應。同時當該自行硬化共聚物於溶液之濃度 超過約50%重量比時,溶液太過黏稠難以處理與控制反應 速率。 υ 任一種已知之聚合起始劑皆可用於自行硬化共聚物之The solvent of the machine is not particularly limited and may be the same as the organic solvent used in the thermosetting resin composition of the present invention. In another aspect, the amount of the organic solvent in the polymerization is controlled so as to be from about 3% to about 50% by weight, for example, about 5, based on the weight of the solution of the self-hardening copolymer in an organic solvent. % to about 30% by weight of the amount present. When the concentration of the self-hardening copolymer in the solution is less than about 3% by weight, the polymerization rate is low, and thus a plurality of monomers remain unreacted. At the same time, when the concentration of the self-hardening copolymer in the solution exceeds about 50% by weight, the solution is too viscous to handle and control the reaction rate.任 Any of the known polymerization initiators can be used for self-hardening copolymers.
合成,包括熱聚合起始劑、光聚合起始劑及氧化還原起始 劑。過氧化物型及偶氮型自由基聚合起始劑可用於本發 明,原因在於容易處理且容易控制反應速率及分子量之故。 可用於本發明之過氧化物型聚合起始劑之實例包括過 15氧化異丁嗣、過氧化環己酮、過氧化甲基環己鋼、過氧化 20 乙醯基丙酮、1,1-貳(第三丁基過氧基)_3,3,5_三曱基環己 烧、1,1-幻第三丁基過氧基)環己院、第三己基過氧 基)-3,3,5-三甲基環己烧、^(第三己基過氧基)環己院、 U-家(第三丁基過氧基)環十二院 '過氧化異丁基、過氧化 月桂酿、過氧化丁二酸、過氧化3,3,5•三甲基㈣、過氧化 笨甲酿、過氧化㈣、過氧化硬㈣、過氧基三碳酸二異 丙醋、過氧基二碳酸二正㈣、過氧基二碳酸二·2乙基己 醋、過氧基二碳酸二-2-乙氧基乙醋、過氧基二碳酸二·2土-甲 乳基丁醋、過氧基二碳酸寒(4_第三丁基環己⑹、⑽武· 15 1378321The synthesis includes a thermal polymerization initiator, a photopolymerization initiator, and a redox initiator. A peroxide type and an azo type radical polymerization initiator can be used in the present invention because it is easy to handle and it is easy to control the reaction rate and molecular weight. Examples of the peroxide type polymerization initiator which can be used in the present invention include isobutyl pentoxide, cyclohexanone peroxide, methylcyclohexyl peroxide, 20 acetoxyacetone peroxide, 1,1-anthracene (Third butylperoxy)_3,3,5-trimethylcyclohexene, 1,1-Penta-t-butylperoxy)cyclohexyl, 3 hexylperoxy)-3,3 , 5-trimethylcyclohexene, ^(Third-hexylperoxy)cyclohexyl, U-home (t-butylperoxy) ring 12th hospital 'isobutyl peroxide, peroxide laurel , succinic acid peroxide, 3,3,5 • trimethyl (4) peroxidation, peroxidized stupid, peroxidized (four), hard (tetra) peroxide, peroxytricarbonate diisopropyl vinegar, peroxydicarbonate Di-n-(4), peroxydicarbonate di-2-ethylhexanoic acid, peroxydicarbonate di-2-ethoxyethyl acetonate, peroxydicarbonate di- 2 soil-methyl lactyl butyl vinegar, peroxygen Dibasic carbonic acid cold (4_t-butylcyclohexyl (6), (10) Wu·15 1378321
新癸醯基過氧基)二異丙苯、過氧基新癸酸異丙苯酯、過氧 基新癸酸辛酯、過氧基新癸酸己酯、過氧基新癸酸第三丁 酯、過氧基特戊酸第三己酯、過氧基特戊酸第三丁酯、2,5-二甲基-2,5-貳(2-乙基己醯基過氧基)己烷、過氧基-2-乙基己 5 酸1,1,3,3-四甲基丁酯、己酸過氧基-2-乙基-第三己酯、己酸 過氧基-2-乙基-第三丁酯、己酸過氧基-2-乙基-第三己酯、 丙酸過氧基-3-甲基-第三丁酯、過氧基月桂酸第三丁酯、過 氧基-3,5,5-三甲基己酸第三丁酯、一碳酸第三己酯過氧基異 丙酯、碳三第三丁酯過氧基異丙酯、2,5-二甲基-2,5-貳(苯 10 甲醯基過氧基)己烷、過乙酸第三丁酯、過苯甲酸第三己 酯、過苯曱酸第三丁酯等及其混合物。過氧化物型聚合起 始劑與還原劑之組合可用作為氧化還原起始劑。 本發明使用之偶氮型聚合起始劑之實例包括1,1-偶氮 貳(環己烷-1-甲腈)、2,2’-偶氮貳(2-甲基-丁腈)、2,2’-偶氮貳 15 丁腈、2,2’-偶氮貳(2,4-二甲基-戊腈)、2,2’-偶氮貳(2,4-二甲 基-4-甲氧基戊腈)、2,2’-偶氮貳(2-脒基-丙烷)鹽酸鹽、2,2’-偶氮貳[2-(5-曱基-2-咪唑啉-2-基)丙烷]鹽酸鹽、2,2’-偶氮貳 [2-(2-咪唑啉-2-基)丙烷]鹽酸鹽、2,2’-偶氮貳[2-(5-甲基-2-咪唑啉-2-基)丙烷]、2,2’-偶氮貳[2-甲基-N-(l,l-貳(2-羥基甲 20 基)-2-羥基乙基)丙醯胺、2,2’-偶氮貳[2-曱基-N-(2-羥基乙基) 丙醯胺]、2,2’-偶氮貳(2-甲基-丙醯胺)二水合物、4,4’-偶氮 貳(4-氰基-戊酸)、2,2’-偶氮貳(2-羥基甲基丙腈)、2,2’-偶氮 貳(2-甲基丙酸)二甲酯(二甲基-2,2’-偶氮貳(2-曱基丙酸 酯))、氰基-2-丙基偶氮甲醯胺等及其混合物。 16 卜 等過氧化物型及偶氮型聚合起始劑之外,於自 二共聚物合成期間,可進一步添加至少一種已知之分 ^控制劑諸如鏈轉㈣、祕結職聚合促進劑來將該 二:硬,共聚物之分子量調整至諸如前文定義之範圍。適 5當分子量控制劑可為疏基丙酸、蔬基丙酸醋、硫甘醇、碰 十一烷基硫醇、α_甲基苯乙烯二聚體等及其混合物。 。於共聚物之製備之有機溶劑以外之一種或多種溶劑 也可添加用於調整組成分溶解度與控制均平性質及控制聚 合後的乾燥速率之目的。 匕外’共聚物可藉已知技術萃取成為固體形式用於純 化、儲存及溶败換目的,該等技術並非限制性諸如喷乾、 薄膜乾燥、滴加入不良溶劑内及再度浸泡。 為了改良耐蝕刻性及耐鹼性與調整流動性,以100份 1 匕自行硬化共聚物為基準,本發明組成物進一步包含聚 (甲基)丙烯酸酯、尼龍、聚酯、聚醯亞胺、或聚矽中之至少 一種聚合物含量為約50份重量比或以下。 進一步可添加熱固催化劑至本發明之熱固性樹脂組成 物。本發明有用之熱固催化劑之實例包括胺化合物、磷化 合物、硼化合物、銻化合物、羧酸化合物、有機磺酸化合 2〇物等及其混合物。為了獲得良好儲存安定性,以1〇〇份重量 比自行硬化共聚物為基準,該熱固催化劑之添加量為約1〇 份重量比或以下。 若有所需,本發明之熱固性樹脂組成物進—步與其它 已知之化學劑諸如抗氧化劑、紫外光安定劑、塑化劑、均 17 1378321 使用本發明之熱固性樹脂組成物所形成之薄膜可施用 至用於影像感應器之一彩色濾光片。 後文將參照下列實例及比較例說明本發明之進一步細 節。但此等實例僅供舉例說明之用而非意圖限制本發明之 5 範圍。 實例 [實例1]Neodecyloxyperoxy)diisopropylbenzene, cumene peroxy neodecanoate, octyl peroxy neodecanoate, hexyl peroxy neodecanoate, third butyl peroxy neodecanoate Ester, third hexyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-indole (2-ethylhexylperoxy) Alkane, peroxy-2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl ester, peroxyperoxy-2-ethyl-trihexyl ester, hexanoic acid peroxy-2 -ethyl-tert-butyl ester, peroxy-2-ethyl-trihexyl hexanoate, peroxy-3-methyl-tert-butyl propionate, tert-butyl peroxy laurate , peroxy-3,5,5-trimethylhexanoic acid tert-butyl ester, monohexyl carbonate monoperoxyisopropyl isopropyl ester, carbon tri-tert-butyl ester peroxyisopropyl ester, 2,5 - dimethyl-2,5-fluorene (benzene 10 mercapto peroxy) hexane, tert-butyl peracetate, third hexyl perbenzoate, tert-butyl perbenzoate, etc. and mixtures thereof . A combination of a peroxide-type polymerization initiator and a reducing agent can be used as the redox initiator. Examples of the azo type polymerization initiator used in the present invention include 1,1-azo (cyclohexane-1-carbonitrile), 2,2'-azobis(2-methyl-butyronitrile), 2,2'-arsenazo 15 butyronitrile, 2,2'-arsenazo (2,4-dimethyl-pentanenitrile), 2,2'-arsenazo (2,4-dimethyl-) 4-methoxyvaleronitrile), 2,2'-arsenazo(2-indolyl-propane) hydrochloride, 2,2'-arsenazo [2-(5-mercapto-2-imidazoline) 2-yl)propane] hydrochloride, 2,2'-arsenazo [2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-arsenazo [2-( 5-methyl-2-imidazolin-2-yl)propane], 2,2'-azo贰[2-methyl-N-(l,l-贰(2-hydroxymethyl 20-yl)-2- Hydroxyethyl)propanamide, 2,2'-arsenazo [2-indolyl-N-(2-hydroxyethyl)propanamide], 2,2'-arsenazo (2-methyl-) Propylamine) dihydrate, 4,4'-arsenazo (4-cyano-pentanoic acid), 2,2'-arsenazo (2-hydroxymethylpropionitrile), 2,2'-even Nitrogen (2-methylpropionic acid) dimethyl ester (dimethyl-2,2'-arsenazo (2-mercaptopropionate)), cyano-2-propylazomethanamine, etc. And mixtures thereof. In addition to the peroxide type and azo type polymerization initiator, at least one known control agent such as chain (four), a secret polymerization accelerator may be further added during the synthesis of the second copolymer. The two: hard, the molecular weight of the copolymer is adjusted to a range such as defined above. The molecular weight controlling agent may be a thioglycolic acid, a vegetable-based propionic acid vinegar, a thioglycol, a non-undecyl mercaptan, an α-methylstyrene dimer, or the like, and a mixture thereof. . One or more solvents other than the organic solvent for the preparation of the copolymer may also be added for the purpose of adjusting the solubility of the component and controlling the leveling property and controlling the drying rate after the polymerization. The ruthenium' copolymer can be extracted into a solid form by conventional techniques for purification, storage, and dissolution. The techniques are not limited, such as spray drying, film drying, dropwise addition to a poor solvent, and re-soaking. In order to improve etching resistance and alkali resistance and adjust fluidity, the composition of the present invention further comprises poly(meth)acrylate, nylon, polyester, polyimine, based on 100 parts of 1 匕 self-hardening copolymer. Or at least one polymer content of the polybenzazole is about 50 parts by weight or less. Further, a thermosetting catalyst may be added to the thermosetting resin composition of the present invention. Examples of the thermosetting catalyst useful in the present invention include an amine compound, a phosphorus compound, a boron compound, a hydrazine compound, a carboxylic acid compound, an organic sulfonated compound, and the like, and a mixture thereof. In order to obtain good storage stability, the thermosetting catalyst is added in an amount of about 1 part by weight or less based on 1 part by weight of the self-hardening copolymer. If desired, the thermosetting resin composition of the present invention can be further formed into a film formed by using the thermosetting resin composition of the present invention with other known chemical agents such as an antioxidant, an ultraviolet stabilizer, a plasticizer, and 17 1378321. Apply to a color filter for one of the image sensors. Further details of the present invention will be described later with reference to the following examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the scope of the invention. Example [Example 1]
於600克丙二醇一甲醚乙酸酯置於裝配有回流冷凝器 及攪動器之1000毫升燒瓶後,以攪拌將溫度升高至80°c。 10 25克甲基丙烯酸縮水甘油酯,13克甲基丙烯酸2-羥基乙 酯,15克曱基丙烯酸,9克甲基丙烯酸9-蔥甲酯,4克N-笨 基順丁烯二醯亞胺,9克苯乙烯,100克甲基丙烯酸甲酯及 20克二曱基-2,2’-偶氮武(2-甲基丙酸醋)之混合物逐滴添加 至燒瓶歷1.5-2小時時間,同時以攪拌將溫度維持於8〇°C。 15 讓所得混合物反應3-4小時伴以攪拌,同時將反應溫度維持 於80°C來獲得含有式7隨機共聚物之溶液。After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 ° C with stirring. 10 25 g of glycidyl methacrylate, 13 g of 2-hydroxyethyl methacrylate, 15 g of methacrylic acid, 9 g of 9-methyl methacrylate, 4 g of N-stupyl butadiene A mixture of amine, 9 g of styrene, 100 g of methyl methacrylate and 20 g of dimercapto-2,2'-azo (2-methylpropionic acid vinegar) was added dropwise to the flask for 1.5-2 hours. Time while maintaining the temperature at 8 °C with stirring. The resulting mixture was allowed to react for 3-4 hours with stirring while maintaining the reaction temperature at 80 ° C to obtain a solution containing the random copolymer of the formula 7.
聚合物溶液之凝膠滲透層析術(GPC)指示基於聚苯乙 烯之基準測定,具有重量平均分子量14,500。 於20克聚合物溶液(a)中添加丨克環氧樹脂(jER_152, JER) ’ 0.05克界面活性劑(R 〇8,mc)及5〇克丙二醇一甲醚 19 1378321 乙酸酯。混合物於充分攪拌溶解及過濾,獲得熱固性樹脂 組成物(e)。 熱固性樹脂組成物(e)使用旋塗機施用至厚0.7毫米玻 璃基材(#1737,康寧公司(Corning)),於乾燥器内於80°C乾 5 燥3分鐘,於230°C硬化30分鐘來製造厚0.5微米之透明薄膜。 [實例2]Gel permeation chromatography (GPC) of the polymer solution indicated a polystyrene based benchmark with a weight average molecular weight of 14,500. To 20 g of the polymer solution (a), a gram epoxy resin (jER_152, JER) '0.05 g of a surfactant (R 〇 8, mc) and 5 g of propylene glycol monomethyl ether 19 1378321 acetate were added. The mixture was dissolved and filtered with thorough stirring to obtain a thermosetting resin composition (e). The thermosetting resin composition (e) was applied to a 0.7 mm thick glass substrate (#1737, Corning) using a spin coater, dried in a drier at 80 ° C for 3 minutes, and hardened at 230 ° C. Minutes to make a transparent film with a thickness of 0.5 microns. [Example 2]
於600克丙二醇一甲醚乙酸酯置於裝配有回流冷凝器 及攪動器之1000毫升燒瓶後,以攪拌將溫度升高至8〇。(:。 30克甲基丙烯酸縮水甘油酯,1〇克甲基丙烯酸2-羥基乙 10酯,15克曱基丙烯酸,5克2-羥基-4-甲基丙烯醯氧基二苯甲 酮,5克N-笨基順丁烯二醯亞胺,β克苯乙烯,5〇克甲基丙 烯酸甲酯及8克二甲基·2,2,_偶氮貳(2-曱基丙酸酯)之混合 物逐滴添加至燒瓶歷1.5-2小時時間,同時以攪拌將溫度維 持於80°C。讓所得混合物反應4_5小時伴以攪拌,同時將反 15應溫度維持於80°C來獲得含有式8隨機共聚物之溶液(b)。After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 8 Torr with stirring. (: 30 g of glycidyl methacrylate, 1 g of 2-hydroxyethyl 10 methacrylate, 15 g of methacrylic acid, 5 g of 2-hydroxy-4-methylpropenyl oxybenzophenone, 5 g of N-styl maleimide, β g of styrene, 5 g of methyl methacrylate and 8 g of dimethyl 2,2,-arsenazo (2-mercaptopropionate) The mixture was added dropwise to the flask for 1.5-2 hours while maintaining the temperature at 80 ° C. The resulting mixture was allowed to react for 4-5 hours with stirring while maintaining the temperature of the reverse 15 at 80 ° C to obtain A solution of the random copolymer of formula 8 (b).
聚合物溶液之凝膠滲透層析術(GPC)指示基於聚苯乙 烯之基準測定,具有重量平均分子量11,000。 以實例1之相同方式製備熱固性樹脂組成物⑺,但使用 4〇克聚合物溶液(b)來替代聚合物溶液⑻。 20 20 根據實例1所述程序製造厚ο.5微米之透明薄膜’但使 用熱固性樹脂組成物(f)替代熱固性樹脂組成物(e)。 [實例3] 於600克丙二醇一甲醚乙酸酯置於裝配有回流冷凝器 及攪動器之1000毫升燒瓶後’以攪拌將溫度升高至80°C。 30克曱基丙稀酸縮水甘油酯,10克甲基丙稀酸2-羥基乙 酯,15克曱基丙烯酸,100克甲基丙烯酸甲酯’ 10克2-(2’-羥基-5’·甲基丙烯醯氧基苯基)苯并三唑,15克N-苯基順丁 烯二醯亞胺,33克苯乙烯,及8克二甲基-2,2’-偶氮貳(2-甲 基丙酸酯)之混合物逐滴添加至燒瓶歷1.5-2小時時間,同時 以攪拌將溫度維持於8(TC。讓所得混合物反應4-5小時伴以 攪拌,同時將反應溫度維持於80°C來獲得含有式9隨機共聚 物之溶液(c)。Gel permeation chromatography (GPC) of the polymer solution indicates a polystyrene based benchmark having a weight average molecular weight of 11,000. The thermosetting resin composition (7) was prepared in the same manner as in Example 1, except that 4 g of the polymer solution (b) was used instead of the polymer solution (8). 20 20 A transparent film of thickness ο. 5 μm was produced according to the procedure of Example 1 except that the thermosetting resin composition (f) was used instead of the thermosetting resin composition (e). [Example 3] After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 ° C with stirring. 30 g of glycidyl acrylate, 10 g of 2-hydroxyethyl methacrylate, 15 g of methacrylic acid, 100 g of methyl methacrylate '10 g of 2-(2'-hydroxy-5' Methyl propylene oxyphenyl) benzotriazole, 15 grams of N-phenyl maleimide, 33 grams of styrene, and 8 grams of dimethyl-2,2'-arsenazo ( A mixture of 2-methylpropionate) was added dropwise to the flask for 1.5-2 hours while maintaining the temperature at 8 (TC). The resulting mixture was allowed to react for 4-5 hours with stirring while maintaining the reaction temperature. A solution (c) containing a random copolymer of the formula 9 was obtained at 80 °C.
聚合物溶液之凝膠滲透層析術(GPC)指示基於聚笨乙 稀之基準測定,具有重量平均分子量9,5〇〇。 以實例1之相同方式製備熱固性樹脂組成物(g ),但使用 40克聚合物溶液(c)來替代聚合物溶液(a)。 根據實例1所述程序製造厚〇5微米之透明薄膜,但使 用熱固性樹脂組成物(g)替代熱固性樹脂組成物卜)。 1378321 [比較例1 ] 於600克丙二醇一甲醚乙竣酯置於裝配有回流冷凝_ 及攪動器之1000毫升燒瓶後,以攪拌將溫度升高至80它。 30克甲基丙稀酸縮水甘油醋’ 13克甲基丙烯酸二環戊酯, 5 12克苯乙烯,25克甲基丙烯酸甲酯及10克二甲基-2,2’-偶氮 貳(2-甲基丙酸酯)之混合物逐滴添加至燒瓶歷15 2小時時 間,同時以攪拌將溫度維持於8(rc ^讓所得混合物反應4_5 小時伴以攪拌,同時將反應溫度維持於8(rc來獲得含有式 10隨機共聚物之溶液(d)。Gel permeation chromatography (GPC) of the polymer solution was determined based on a polystyrene standard with a weight average molecular weight of 9,5 Å. The thermosetting resin composition (g) was prepared in the same manner as in Example 1, except that 40 g of the polymer solution (c) was used instead of the polymer solution (a). A transparent film of 5 μm thick was produced according to the procedure described in Example 1, except that the thermosetting resin composition (g) was used instead of the thermosetting resin composition. 1378321 [Comparative Example 1] After 600 g of propylene glycol monomethyl ether acetate was placed in a 1000 ml flask equipped with a reflux condenser and an agitator, the temperature was raised to 80 with stirring. 30 g of methacrylic acid glycidol vinegar '13 g of dicyclopentanyl methacrylate, 5 12 g of styrene, 25 g of methyl methacrylate and 10 g of dimethyl-2,2'-arsenazo ( A mixture of 2-methylpropionate) was added dropwise to the flask over a period of 15 hours, while maintaining the temperature at 8 with stirring (rc^ allowing the resulting mixture to react for 4-5 hours with stirring while maintaining the reaction temperature at 8 ( Rc to obtain a solution (d) containing a random copolymer of the formula 10.
聚合物溶液之凝膠滲透層析術(GPC)指示基於聚苯乙 烯之基準測定,具有重量平均分子量13,000。 以實例1之相同方式製備熱固性樹脂組成物(h ),但使用 40克聚合物溶液(d)來替代聚合物溶液(a)。 15 根據實例1所述程序製造厚0.5微米之透明薄膜,但使 用熱固性樹脂組成物(h)替代熱固性樹脂組成物⑷。 <物理性質之評估> *根據下列個別程序評估實例i至3及比較例i製造之透 月薄膜之平坦度、黏著性、薄膜硬度及透光率 2〇施用至各透明膜,桩牮制 边月膜接者製作圖樣。計算由於各項不良因素 例如光晕效應所造成的圖樣缺陷數目。結果顯示於幻/、 22 1378321Gel permeation chromatography (GPC) of the polymer solution indicates a polystyrene based benchmark having a weight average molecular weight of 13,000. The thermosetting resin composition (h) was prepared in the same manner as in Example 1, except that 40 g of the polymer solution (d) was used instead of the polymer solution (a). 15 A transparent film of 0.5 μm thick was produced according to the procedure described in Example 1, except that the thermosetting resin composition (h) was used instead of the thermosetting resin composition (4). <Evaluation of physical properties> * The flatness, adhesion, film hardness and light transmittance of the moon-transparent film manufactured in Examples i to 3 and Comparative Example i were evaluated according to the following individual procedures. The side moon film picker makes the pattern. Calculate the number of pattern defects caused by various adverse factors such as halo effect. The result is displayed in illusion /, 22 1378321
①平坦度之評估 測量虛設彩色濾光片之紅像素與綠像素之中心部分間 之问度差異(亦即像素間之階級高度)。於實例丨至3及比較例 1所製造之各透明膜施用至該虛設彩色濾光片後,測量彩色 濾光片之像素間之階級尚度<»施用透明膜前之階級高度(dl) 對施用透明膜後之階級高度(d2)之比R係以方程式(1)計算 如下: R= d2/dl......⑴ 實例1至3及比較例1所製備之熱固性樹脂組成物之平 10坦化效能基於下列標準分成五級:r>〇.4···等級1 ; 〇.4紐郊.3…等級2 ; 0W0.3...等級3 ; 0.2^0丄·等級4 ; R<0.1...等級5。 等級愈高,則平坦化效能愈佳。 ②黏著性及耐化學性測試 15 於實例1至3及比較例1所製造之各透明薄膜上劃割十 字長條形的1 〇〇個十字交又切割後,使用賽璐芳(cell〇phane) 膠帶進行撕離測試(十字切割測試)。視覺檢驗檢查十字切割 的撕離狀態來評估透明薄膜之黏著性。當無任何十字切割 被撕離時,黏著性判定為「合格」。當有一個或多個十字切 20割被撕離時,黏著性判定為「不合格」。 此外,透明薄膜試驗件分別浸泡於N_甲基_2_β比略咬_ (ΝΜΡ)作為有機溶劑,10%水性鹼性氫氧化鉀溶液及酸性蝕 刻劑〉谷液(LCE-12K,赛恩泰克公司(cyantEK CORPORATION))於40 C浸泡30分鐘後’重複前述黏著性測 23 1378321 試程序來評估化學耐性。觀察十字切割之撕離狀態。當於 各次浸泡後無任何十字切割被撕離時,化學耐性判定為「合 格j。當於各次浸泡後有一個或多個十字切割被撕離時,化 學耐性判定為「不合格」。 5 ③薄膜硬度之評估 實例1至3及比較例1所製造之透明膜使用6種(1H-6H) 鉛筆(史達樂(Statdler))刮擦後,觀察薄膜損害情況。根據損 害程度將薄膜強度分成六級(1H-6H)。1 Flatness evaluation Measures the difference between the red and green pixels of the dummy color filter (that is, the class height between pixels). After applying the transparent films manufactured in Examples 丨 to 3 and Comparative Example 1 to the dummy color filter, measuring the order between the pixels of the color filter <»the height of the class before applying the transparent film (dl) The ratio R of the class height (d2) after application of the transparent film is calculated by the following equation (1): R = d2 / dl (1) Thermosetting resin compositions prepared in Examples 1 to 3 and Comparative Example 1 The flattening performance is divided into five levels based on the following criteria: r>〇.4···level 1; 〇.4 New suburbs.3...level 2; 0W0.3...level 3; 0.2^0丄·grade 4; R<0.1...level 5. The higher the rating, the better the flattening performance. 2Adhesion and chemical resistance test 15 After cutting one cross and cutting the cross-shaped strips on each of the transparent films manufactured in Examples 1 to 3 and Comparative Example 1, use cell 〇 璐The tape is peeled off (cross cut test). The visual inspection checks the tear-off state of the cross-cut to evaluate the adhesion of the transparent film. When no cross cut was torn off, the adhesion was judged as "acceptable". When one or more cross cuts are torn off, the adhesion is judged as "failed". In addition, the transparent film test pieces were immersed in N_methyl 2_β ratio slightly bite _ (ΝΜΡ) as an organic solvent, 10% aqueous alkaline potassium hydroxide solution and acidic etchant> gluten solution (LCE-12K, Saintek) The company (cyantEK CORPORATION) was immersed in 40 C for 30 minutes to 'repeat the aforementioned adhesion test 23 1378321 test procedure to evaluate chemical resistance. Observe the tearing state of the cross cut. When no cleavage was torn off after each immersion, the chemical resistance was judged as "commendation j." When one or more cross-cuts were torn off after each immersion, the chemical resistance was judged as "failed". 5 3 Evaluation of film hardness The transparent films produced in Examples 1 to 3 and Comparative Example 1 were scratched using six kinds of (1H-6H) pencils (Statdler), and the film damage was observed. The film strength was divided into six levels (1H-6H) depending on the degree of damage.
□圖樣缺陷(藉光暈現象)之評估 10 CMOS影像感應器之彩色光阻施加至實例1至3及比較 例1所形成之各透明膜上,照光及顯影來形成圖樣。觀察圖 樣之形狀。計算由圖樣邊界凸起的缺陷數目。圖樣缺陷係 由於來自於下方基材反射紫外光所造成,如第2圖所示。使 用比較例1及實例1所製造之透明膜形成之圖樣形狀分別顯 15 示於第3圖及第4圖。□ Evaluation of pattern defects (by halo phenomenon) 10 The color photoresist of the CMOS image sensor was applied to each of the transparent films formed in Examples 1 to 3 and Comparative Example 1, and illuminated and developed to form a pattern. Observe the shape of the pattern. Calculate the number of defects that are raised by the border of the pattern. The pattern defect is caused by the reflection of ultraviolet light from the underlying substrate, as shown in Figure 2. The pattern shapes formed by using the transparent films produced in Comparative Example 1 and Example 1 are shown in Figs. 3 and 4, respectively.
物理性質 實例1 實例2 實例3 比較例1 平坦度 合格 合格 合格 合格 黏著性(十字切割) 100/100 100/100 100/100 95/100 薄膜硬度(鉛筆硬度) 4H 5H 4H 2H 酸 合格 合格 合格 合格 化學耐性 鹼 合格 合格 合格 不合格 有機溶劑 合格 合格 合格 不合格 365奈米 86.2% 91.7% 90.5% 99.5% 透光率 400奈米 98.6% 99.5% 99.2% 99.8% 圖樣缺陷 3/100 8/100 7/100 27/100 24 1378321 由表1结果可知,就平坦杜、黏著性、於可見光區之透 光率及薄膜硬度等方面而言,使用實例1至3所製造之熱固 性樹脂組成物製造之透明膜顯示優異特性。例如薄膜對可 見光區輻射的通過實質上為透明,例如具有於波長400奈米 5 之可見光輻射之最小透光率至少約98%。此外,透明膜吸 收紫外光365奈米,促成圖樣缺陷數目的顯著減少。例如本 發明薄膜具有於波長365奈米之輻射之最大透射率約為 92%。Physical Properties Example 1 Example 2 Example 3 Comparative Example 1 Flatness Qualified Qualified Adhesiveness (Cross Cut) 100/100 100/100 100/100 95/100 Film Hardness (Pencil Hardness) 4H 5H 4H 2H Acid Qualified and Qualified Chemically resistant alkali qualified qualified unqualified organic solvent qualified qualified unqualified 365 nm 86.2% 91.7% 90.5% 99.5% Light transmittance 400 nm 98.6% 99.5% 99.2% 99.8% Pattern defect 3/100 8/100 7/ 100 27/100 24 1378321 It can be seen from the results of Table 1 that the transparent film made of the thermosetting resin composition produced in Examples 1 to 3 was used in terms of flatness, adhesion, light transmittance in the visible light region, and film hardness. Shows excellent features. For example, the film is substantially transparent to the passage of visible light region radiation, e.g., has a minimum light transmission of at least about 98% of visible light radiation having a wavelength of 400 nm. In addition, the transparent film absorbs 365 nm of ultraviolet light, contributing to a significant reduction in the number of pattern defects. For example, the film of the present invention has a maximum transmittance of about 92% of radiation at a wavelength of 365 nm.
由前文說明顯然易知,本發明之熱固性樹脂組成物容 10 易處理,具有比較習知用於製造彩色濾光片之二部分式熱 固性樹脂組成物更佳的化學财性。此外,使用本發明之熱 固性樹脂組成物所製造之彩色濾光片用之透明膜具有絕佳 平坦度、黏著性、透射率、薄膜強度及耐熱性。此外,本 發明之熱固性樹脂組成物可吸收紫外光。因此,當本發明 15 之熱固性樹脂組成物用於製造影像感應器之彩色濾光片 時,可減少因再度反射的紫外光之光暈及駐波所造成的圖 樣缺陷數目。 熟諳本發明技藝人士由前文說明之教示獲益,多項本 發明之修改及其它實施例將顯然自明。因此須了解本發明 20 並非囿限於所揭示之特定實施例,修改例及其它實施例意 圖含括於隨附之申請專利範圍。雖然於此處採用特定術 語,但只以概略說明意義使用絕非限制性,本發明之範圍 係如申請專利範圍界定。 < S ) 25 1378321 I:圖式簡單說明3 第1圖為示意圖顯示CMOS影像感應器之結構。 第2圖為示意圖顯示藉光反射出現圖樣缺陷之機轉。 第3圖顯示經由將一CMOS影像感應器用之一彩色光阻 施用至比較例1所形成之一透明膜,將該彩色光阻曝光及顯 影曝光後之彩色光阻所得之一圖樣形狀。As apparent from the foregoing description, the thermosetting resin composition of the present invention is easy to handle, and has a better chemical property than the two-part thermosetting resin composition conventionally used for producing a color filter. Further, the transparent film for a color filter produced by using the thermosetting resin composition of the present invention has excellent flatness, adhesion, transmittance, film strength and heat resistance. Further, the thermosetting resin composition of the present invention can absorb ultraviolet light. Therefore, when the thermosetting resin composition of the present invention 15 is used for the color filter of the image sensor, the number of pattern defects caused by the halo and standing waves of the re-reflected ultraviolet light can be reduced. It will be apparent to those skilled in the art that <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Therefore, it is to be understood that the invention is not limited to the specific embodiments disclosed, and the modifications and other embodiments are intended to be included in the scope of the appended claims. Although specific terms are employed herein, the use of the invention is in no way limiting, and the scope of the invention is defined by the scope of the claims. <S) 25 1378321 I: Simple description of the drawing 3 Fig. 1 is a schematic view showing the structure of a CMOS image sensor. Figure 2 is a schematic diagram showing the machine rotation of the pattern defect caused by light reflection. Fig. 3 shows a pattern shape obtained by applying a color resist of a CMOS image sensor to a transparent film formed in Comparative Example 1, and exposing and exposing the color resist to a color resist.
第4圖顯示經由將一 CMOS影像感應器用之一彩色光 阻施用至實例1所形成之一透明膜,將該彩色光阻曝光及顯 影曝光後之彩色光阻所得之一圖樣形狀。 10 【主要元件符號說明】 (無)Fig. 4 shows a pattern shape obtained by applying a color refractory film of a CMOS image sensor to a transparent film formed in Example 1, and exposing and developing the color resist of the color resist. 10 [Main component symbol description] (none)
< S ) 26< S ) 26
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KR102216766B1 (en) * | 2018-11-23 | 2021-02-16 | 주식회사 엘지화학 | Photosensitive resin composition, photoresist, color filter and display device |
CN112708019B (en) * | 2019-10-25 | 2024-04-30 | 乐凯化学材料有限公司 | Water-soluble color stabilizer for color photographic paper and preparation method thereof |
KR102679740B1 (en) | 2022-01-25 | 2024-06-28 | 케이피엑스케미칼 주식회사 | One-component thermosetting resin composition and function membrane comprising the same |
WO2024029204A1 (en) * | 2022-08-03 | 2024-02-08 | 住友化学株式会社 | Colored curable resin composition, color filter, display device, and solid-state image pickup element |
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US5919601A (en) | 1996-11-12 | 1999-07-06 | Kodak Polychrome Graphics, Llc | Radiation-sensitive compositions and printing plates |
KR100493961B1 (en) * | 1999-08-17 | 2005-06-10 | 주식회사 엘지화학 | Photosensitive resin composition |
KR100442865B1 (en) | 2001-11-07 | 2004-08-02 | 삼성전자주식회사 | Photosensitive polymer having fluorinated ethylene glycol group and chemically amplified resist composition comprising the same |
KR100574956B1 (en) * | 2003-11-20 | 2006-04-28 | 삼성전자주식회사 | Voltage reference clock generating circuit capable of generating voltage reference clock synchronized with system clock and method thereof |
JP4864375B2 (en) * | 2004-08-09 | 2012-02-01 | ドンジン セミケム カンパニー リミテッド | Photosensitive resin composition for spacer, spacer and liquid crystal display element |
KR100642446B1 (en) * | 2004-10-15 | 2006-11-02 | 제일모직주식회사 | Thermosetting One-Solution Type Composition For Protective Film Of Color Filter And Color Filter By Using The Same |
KR100866718B1 (en) * | 2005-06-17 | 2008-11-05 | 도판 인사츠 가부시키가이샤 | Imaging element |
KR100805688B1 (en) * | 2005-09-15 | 2008-02-21 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
JP2007090782A (en) * | 2005-09-29 | 2007-04-12 | Dainippon Printing Co Ltd | Protective layer transfer sheet, and printed object |
JP4421566B2 (en) * | 2005-12-26 | 2010-02-24 | チェイル インダストリーズ インコーポレイテッド | Hard mask composition for photoresist underlayer film and method of manufacturing semiconductor integrated circuit device using the same |
KR100758879B1 (en) * | 2006-07-13 | 2007-09-14 | 제일모직주식회사 | One-solution type thermosetting composition for protective film of color filter |
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2007
- 2007-06-19 KR KR1020070059842A patent/KR100835605B1/en active IP Right Grant
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2008
- 2008-01-31 JP JP2008021344A patent/JP4726917B2/en active Active
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CN101329420B (en) | 2010-10-13 |
CN101329420A (en) | 2008-12-24 |
JP4726917B2 (en) | 2011-07-20 |
KR100835605B1 (en) | 2008-06-09 |
JP2009001770A (en) | 2009-01-08 |
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