TW200944940A - Negative resist composition - Google Patents
Negative resist composition Download PDFInfo
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- TW200944940A TW200944940A TW098110026A TW98110026A TW200944940A TW 200944940 A TW200944940 A TW 200944940A TW 098110026 A TW098110026 A TW 098110026A TW 98110026 A TW98110026 A TW 98110026A TW 200944940 A TW200944940 A TW 200944940A
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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
- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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Abstract
Description
200944940 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於顯示器之負型光阻組合物，特別 地’係關於一種具有優異的耐熱性及抗吸濕性能之負型光阻組 合物’其能夠藉由鹼性顯影劑顯影以形成液晶顯示器之R GB. 彩色滅光片、黑色矩陣、間隔物、紫外光保護層或有機絕緣膜 及其類似物之圖案。 【先前技術】 ❹200944940 VI. Description of the Invention: [Technical Field] The present invention relates to a negative-type photoresist composition for a display, in particular, to a negative-type photoresist having excellent heat resistance and moisture absorption resistance. The composition 'can be developed by an alkali developer to form a pattern of R GB. color extinction sheet, black matrix, spacer, ultraviolet protective layer or organic insulating film and the like of the liquid crystal display. [Prior Art] ❹
尤丨且劑可用於形成液晶顯示器之R. G. B.彩色濾光片、黑色 矩陣、間隔物、紫外光保護層或有機絕緣膜及其類似物之圖 案。邊光阻劑應具有優異的平坦度、穿透率、财熱性、耐化學 性及抗吸濕性能。近來，—種用於RGB彩色濾光片、黑色矩 陣、。間隔物、紫外光保護層或有機絕緣膜之丙烯基光阻劑在 22^C^低於220。〇之製程中於可見光區域顯示出95%或高於 娜^穿透率。然、而’該丙烯基光阻劑在23(rc或高於23〇 C之面溫製程巾具有低熱穩定性，因此—部分細旨受熱分解。 結果，降低了該光阻劑在可見光區域之穿透率，並且在高溫製 程中分解產生之分子可能污染液晶顯示器。以及，在藉由含水 顯影麵f彡過財，麵職光_由於減翻旨之酸性組分 ΠΓίί容Γ所吸附之水可能污染液晶顯示器和薄膜電晶體。 «又a十本發明以解決該等問題。因此’本發明之— ΓΐΪ在1^溫下具有健的抗韻性能及<舰之貞型光阻 =陣從:可容易地形成R.G轉色遽光片之彩色光二 … 柱關_、絕緣細或賴層之圖案。 為了達到上述目標，根據本發明之負型光阻組合物包括一 3 200944940 藉=下述化學式1麵之黏結樹脂；―多官能基（曱基）丙稀 基單體；一光引發劑；以及一有機溶劑： 【化學式1】 其中A為-藉由含有3至1〇個碳原子之環氧基取代之 基）丙烯酸酯單體所形成之重複單元，以及 ^為-藉由下述化學式2絲之絲醯胺酸單體所形成之 重複半兀· 0 % %：The enamel agent can be used to form a pattern of a R. G. B. color filter, a black matrix, a spacer, an ultraviolet protective layer or an organic insulating film and the like of a liquid crystal display. The edge photoresist should have excellent flatness, transmittance, heat, chemical resistance and moisture absorption resistance. Recently, it has been used for RGB color filters, black matrices, and the like. The spacer, the ultraviolet protective layer or the organic insulating film of the propylene-based photoresist is lower than 220 at 22 ° C. In the process of enamel, it shows 95% or higher penetration rate in the visible light region. However, 'the propylene-based photoresist has a low thermal stability at 23 (rc or higher than 23 ° C), so part of the purpose is thermally decomposed. As a result, the photoresist is reduced in the visible region. The penetration rate, and the molecules generated by the decomposition in the high-temperature process may contaminate the liquid crystal display, and the water absorbed by the aqueous developing surface, due to the reduction of the acidic component ΠΓίίΓ It may contaminate the liquid crystal display and the thin film transistor. «A ten invention to solve these problems. Therefore, the present invention has a robust anti-rhythm performance at the temperature of 1^ and a ship's 光-type resist = array From: The color light of the RG color-changing calender can be easily formed... The pattern of the pillars _, the insulating layer or the lamella layer. In order to achieve the above object, the negative-type photoresist composition according to the present invention includes a 3 200944940 a bonding resin of the chemical formula 1; a polyfunctional (fluorenyl) acryl monomer; a photoinitiator; and an organic solvent: wherein A is - by containing 3 to 1 carbon atom Epoxy-substituted group) acrylate single The repeating unit formed by the body, and ^ is - a repeating half 兀· 0 % % formed by the methic acid monomer of the following formula 2:
Rf—X_ 其中’ Ri ’ R4和R5各自獨立地為氫、具有丨至1〇個碳 之烧基或環絲、苯錢絲基，以％各自獨域為氮或甲 基，以及X為〇或s，以及 〆 n C為-能夠發生自由絲合之單體所形成之重複單元，該 =體諸如藉由含有丨錢個销子之絲或環絲、苯基或节 f取代或未取代之（甲基）丙烯酸酯、（甲基）丙婦酸或（甲 ❹ 胺；藉由含有1至1G個碳原子找基或苯基在顺 ^取代或未取代讀絲（苯基）馬來酿亞胺或N(祕）苯 亞胺；藉由含有㈤個碳原子之絲、乙稀基或乙醯 ^ 2代或未取代之苯乙稀或（_丙稀猜；含有3至12個 ”絲乙烯細’·或含有3至12個碳原子之烧基 酯’或彼等之混合物。 _其1 ’以化學式1中各個重複單元之莫耳比計，X為0纖 〇·60，y_.02至0.50,以及Z為0.05至0.70。 根據本發明之黏結樹脂之重均分子量為！，〇〇〇至獅，麵， 多为散性為1.G至動。該黏結樹脂可為具有無規安排之重複單 200944940 元之無規共聚物’然而本發明並不限於此方面。 該負型光阻組合物可包括基於該負型光阻組合物之總重 量計之3至50重量％之黏結樹脂、2至4〇重量％之多官能基（曱 基）丙烯基單體、〇.〇1至10重量％之光引發劑以及剩餘量之有 機溶劑，然而本發明並不限於此方面。 【實施方式】 在下文中，將對本發明進行詳細描述。在該描述之前，應 瞭解，在本說明書及附加申請專利範圍中使用之術語不應限於 e 用一般及詞典之含義進行解釋，而是基於允許發明者適當地定 • 義術語最側述之刺’根據穌發明之細方面相應 之含義及概念進行理解。 w • 在上述化學式1巾’ A為藉由一具有3至10個碳原子之環氧 基取代之（甲基）丙烯酸酯單體所形成之重複單元，其在該黏 結樹脂共聚物中之含量為3至60莫耳％。例如，該藉由一具有3 至10個碳原子之環氧基取代之（甲基）力稀酸醋可為：（^) 丙烯酸縮水甘油酯、縮水甘油基_α_丙烯酸甲酯、縮水甘油1 _α-丙烯酸乙酯、縮水甘油基-α-丙烯酸丁酯、3,4·環氧其甲 基）丙烯酸丁酯、6,7-環氧基曱基丙烯酸庚酯、6,7_環$基丙 稀酸庚酉旨、6,7-環氧基庚基普丙烯酸甲醋、2_縮水甘油基&義 •1·丙烯酸丙g旨、2,3-環氧基（甲基）丙烯酸環己醋、3 4環& 基（甲基）丙稀酸環己醋、3-甲基氧雜環丁燒_3·甲基丙稀 醋或3_乙基氧雜環丁烧_3_甲基丙烯酸甲醋，其可單獨或混合地 使用’然而本發明並不限於此方面。 σ 在上述化學式1中，Β為-藉由上述化學式2表示之馬來酿 胺酸基單體所形成之重複單元，且在該黏結樹脂共聚物中^ 量為2至5G莫耳％。較佳地’該絲_縣物具料至職 5 200944940 碳原子。在上述化學式2中’ Rl，1及&各自獨立地為氫且 有1至10個碳原子之烧基或環絲、苯基、或鮮基，心及^ 各自獨立地為氫或甲基’以及X為〇或s。 在上述化學式2中，例如，Rl，r^r5各自獨立地為氮、 甲基、乙基、丙基、丁基、異丙基、戊基、己基、環己基、癸 基、經乙基、苯基、苄基或羥苯基，然而本發明並不限於此方 面。 在上述化學式1中，C為一能夠發生自由基聚合之單體所 形成之重複單元，其在該共聚物中之含量為5至70莫耳％。較 佳地，具有重複單元C之單體可為一具有3至14個碳原子及不 飽和雙鍵之化合物或彼等之混合物，例如，藉由含有丨至1〇個 碳原子之烷基或環烷基、苯基或苄基取代或未取代之（曱基） 丙烯酸酯、（甲基）丙烯酸或（甲基）丙烯醯胺；藉由含有1 至10個碳原子之烷基或苯基在N位置取代或未取代之N•烷基 (苯基）馬來醯亞胺或N-(經基）苯基馬來醯亞胺；藉由含有 1至6個碳原子之烷基、乙烯基或乙醯氧基取代或未取代之苯乙 烯或（甲基）丙烯腈；具有3至12個碳原子之烷基乙烯基醚； 或具有3至12個碳原子之烷基乙烯基酯，其可單獨或混合地使 用’然而本發明並不限於此方面。 特別地，具有重複單元C之單體可為：（曱基）丙烯酸、 (甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸 丙酯、（曱基）丙烯酸丁酯、（甲基）丙烯酸戊酯、（甲基） 丙烯酸己酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸異冰片 醋、（甲基）丙烯酸金剛烧酯、（甲基）丙烯酸二環戊酯、（甲 基）丙烯酸二環戊烯酯、（甲基）丙烯酸苄酯、（甲基）丙烯 酸2-甲氧基乙酯、（甲基）丙烯酸羥乙酯、（甲基）丙烯酸2_ 丙烯醯胺 、N-甲基（f基）丙烯醯胺、Rf—X_ wherein ' Ri ' R4 and R5 are each independently hydrogen, a ruthenium or ruthenium having 1 to 10 carbons, or a benzyl group, each of which is independently nitrogen or methyl, and X is 〇 Or s, and 〆n C is - a repeating unit formed by a free-spinning monomer, such as substituted or unsubstituted by a filament or a loop, a phenyl or a f-fed containing a pin (meth) acrylate, (meth) propyl benzoate or (methanoamine; by looking for a group containing 1 to 1 G carbon atoms or a phenyl group in a cis-substituted or unsubstituted read (phenyl) Malay An imine or N (small) phenylimine; by containing (f) a carbon atom, a vinyl group or an ethyl bromide or an unsubstituted styrene or (_ propylene guess; containing 3 to 12 "Silkethylene fine" or a mixture of 3 to 12 carbon atoms or a mixture thereof. _1' is in the molar ratio of each repeating unit in Chemical Formula 1, X is 0 〇·60, Y_.02 to 0.50, and Z is 0.05 to 0.70. The weight average molecular weight of the bonding resin according to the present invention is !, to the lion, the surface, and the bulk is 1.G to the dynamic. The bonding resin can be With Random arrangement of the random copolymer of 200944940 yuan. However, the invention is not limited in this respect. The negative photoresist composition may comprise 3 to 50% by weight based on the total weight of the negative photoresist composition. a binder resin, 2 to 4% by weight of a polyfunctional (fluorenyl) propylene-based monomer, 1 to 10% by weight of a photoinitiator, and a remaining amount of an organic solvent, although the invention is not limited in this respect. [Embodiment] Hereinafter, the present invention will be described in detail. Before the description, it should be understood that the terms used in the specification and the appended claims should not be limited to the meaning of the general and dictionary meanings, but Based on the understanding that the inventor appropriately defines the terminology of the terminology, it is understood according to the corresponding meanings and concepts of the fine aspects of the invention. w • In the above chemical formula, the towel A has a carbon atom of 3 to 10 carbon atoms. The repeating unit formed by the epoxy group-substituted (meth) acrylate monomer is contained in the binder resin copolymer in an amount of from 3 to 60 mol%. For example, the one having from 3 to 10 The (meth) dilute acid vinegar substituted with an atomic epoxy group may be: (^) glycidyl acrylate, glycidyl _α_methyl acrylate, glycidol 1 _α-ethyl acrylate, glycidyl-α - butyl acrylate, 3,4·epoxymethyl) butyl acrylate, 6,7-epoxyheptyl decyl hexyl acrylate, 6,7-cyclo-glycolic acid, 6,7- Epoxy heptyl propyl methacrylate, 2 _ glycidyl group & 1:1 acrylate, 2,3-epoxy (cyclo) methacrylate, 3 4 ring & base (A Base propylene hexanoic acid acrylate, 3-methyl oxetane _3·methyl propylene vinegar or 3-ethyl oxetane _3_methacrylic acid methyl vinegar, which can be used alone or in combination Use ' However, the invention is not limited in this respect. σ In the above Chemical Formula 1, Β is a repeating unit formed by the maleic acid-based monomer represented by the above Chemical Formula 2, and is 2 to 5 Gmol% in the bonded resin copolymer. Preferably, the silk _ county material has the right to serve 5 200944940 carbon atoms. In the above Chemical Formula 2, 'Rl, 1 and & are each independently a hydrogen and have 1 to 10 carbon atoms of a burnt or cyclofilament, a phenyl group, or a fresh base, and the cores and each are independently hydrogen or methyl. 'And X is 〇 or s. In the above Chemical Formula 2, for example, R1, r^r5 are each independently nitrogen, methyl, ethyl, propyl, butyl, isopropyl, pentyl, hexyl, cyclohexyl, decyl, ethyl, Phenyl, benzyl or hydroxyphenyl, however the invention is not limited in this respect. In the above Chemical Formula 1, C is a repeating unit formed of a monomer capable of undergoing radical polymerization, and its content in the copolymer is 5 to 70 mol%. Preferably, the monomer having a repeating unit C may be a compound having 3 to 14 carbon atoms and an unsaturated double bond or a mixture thereof, for example, an alkyl group having from 丨 to 1 carbon atom or a cycloalkyl, phenyl or benzyl substituted or unsubstituted (fluorenyl) acrylate, (meth)acrylic acid or (meth) acrylamide; by an alkyl group having 1 to 10 carbon atoms or a phenyl group Substituted or unsubstituted N•alkyl(phenyl)maleimide or N-(trans)phenylmaleimide at the N position; by alkyl group having 1 to 6 carbon atoms, ethylene a styrene or (meth)acrylonitrile substituted or unsubstituted with an ethoxy group; an alkyl vinyl ether having 3 to 12 carbon atoms; or an alkyl vinyl ester having 3 to 12 carbon atoms, It can be used singly or in combination 'however, the invention is not limited in this respect. In particular, the monomer having the repeating unit C may be: (mercapto)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate , (meth) pentyl acrylate, (meth) hexyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantate (meth) acrylate, (meth) acrylate Cyclopentyl ester, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid 2_ acrylamide, N-methyl (f-) acrylamide,
200944940 乙氧基乙酯、（甲基） ，來醯亞胺、N_甲基馬來酿亞胺、N_乙基馬來酿亞胺、 ，來醯亞胺、N_丁基馬來醯亞胺、N_環己基馬來酿亞胺、 ^戊基馬來酿亞胺、N-鮮基馬來醯亞胺、苯乙婦、心甲美 =乙婦、乙酿氧基苯乙稀、（甲基）丙稀腈、己基乙朗或= 酸乙烯酯，其可單獨或混合地使用。 較佳地，藉由根縣發明之上雜學式丨表示之黏結樹脂 之重均分子量為I000至，〇〇〇,分散性為1.0至1〇.〇，更佳地， 其重均分子量為4,00〇至1⑻，000，分散性為1.5至3.0。 具有化學式1之黏結樹脂是一種共聚物，並且可以是一種 具有無規鋪之重複單元之無規共雜，然而本發明並不限於 此方面。 ' 在本發明之負型光阻組合物中，該黏結樹脂之含量可根據 需要適當地進行控制，例如，基於該組合物總重量計之3至50 重量％。 在本發明之負型光阻組合物中，該具有至少一個丙烯基之 多官能基（甲基）丙烯基單體可為，例如，一酯類化合物、一 種藉由二每甲基與丙烧三縮水甘油趟丙烯酸進行加成反應之 產物、或者一種藉由鄰苯二甲酸酐與一藉由酚醛環氧樹脂及 (甲基）丙稀酸加成反應所得之產物進行加成反應而製備之紛 醛型環氧丙烯酸樹脂，或彼等之混合物。該酯類化合物包括具 有2至20個環氧乙烷基之聚乙二醇二（甲基）丙烯酸酯、乙二 醇二（甲基）丙烯酸酯、具有2至14個環氧丙烷基之聚丙二醇 二（甲基）丙烯酸酯、丙二醇二（甲基）丙烯酸酯、三羥曱基 丙烧二（甲基）丙烯酸酯、一種藉由雙紛A與二縮水甘油醚丙 烯酸進行加成反應之產物、異氰脲酸三（甲基）丙烯酸乙酯、 7 200944940 (甲基）丙烯酸点-羥乙酯之鄰苯二甲酸二酯、—種藉由（甲 基）丙烯酸/3-經乙醋與甲苯二異氰酸g旨進行加成反應之產 物、三羥甲基丙烷三（甲基）丙烯酸醋、四羥甲基甲烷四（甲 基）丙稀酸醋、異戊四醇三（甲基）丙婦酸醋、異戊四醇四（甲 基）丙烤酸酯、二異戊四醇五（甲基）丙婦酸醋、二異戊四醇 六（甲基）丙烯酸S旨及二異細醇三（甲基）丙稀酸醋。 可根據需要適當控制該多官能基（甲基）丙婦基單體之含 量，例如，基於該組合物總重量計之2至4〇重量％，然而本發 明並不限於此方面。在該多官能基（甲基）丙歸酸單體之含量 屬於上述提及之範圍時，在曝光部分之薄膜經曝光及顯 後保持良好’薄膜之交聯程度保持撼佳水平，因此該薄膜之 性能及熱穩定性可良好地保持。 ' 可根據本發明適當控制多官能基（？基）丙婦基單體餘 結樹脂之組分比’從而製備一種能夠保持薄膜彈性、耐化學性 及圖案穩定性之負型光阻組合物。 以及’根據本發明之負型光阻組合物中所包括之光引發劑 可為通常使用之苯乙酮基衍生物、二苯甲酮基衍生物或肟衍生 物。若該光引發劑自身具有顏色，則穿透率會降低。較佳地， 該引發劑在曝光製程所使用之波長範圍内具有適合之靈敏度 且無色’從而導致高穿透率。因此，在藉由使用該多官能基（甲 基）丙烯基單體進行交聯反應製備本發明之負型光阻組合物 中應考慮所使用之紫外光波長以適當地選擇所使用之光引發 劑。在通常使用汞燈之情形下，較佳地使用一可在31〇至45〇 奈米之汞燈之紫外波長下可產生自由基之光引發劑。 —例如，該光引發劑可為三苯基氧化膦、二苯曱酮、苯基聯 笨基酮、1-羥基-1-苯甲醯基環己烷、苄基二甲基縮酮、苄基 200944940 一甲基胺(4-嗎琳基-苯甲醯基）丙烧、2-嗎琳基_2_ (4· 甲基疏基）苯曱酿基丙燒、奮頻酮、1-氯-4-丙基喧嘴酿j、異兩 基噻噸酮、二乙基噻噸酮、乙基蒽醌、4-苯甲醯基_4_甲基二笨 基硫化物、苯甲醯基丁基醚、2-羥基-2-苯甲醯基丙烷、2_經基 -2- (4-異丙基）苯甲醯基丙烷、4-丁基苯甲醯基三氯甲燒、: 苯氧基苯曱醯基二氯甲烷、甲基苯甲醯基甲酸、丨，7_雙（9_3丫 啶基）庚院、9-正丁基-3,6-雙（2-嗎琳基異丁醯基）σ弄哇、 甲基_4,6·雙（二氟甲基）-s-三嗪、2-苯基_4,6_雙（三氯甲基） ❹ s 一秦、2-秦基-4,6-雙（二氯甲基）-s-三嗓、2·节基-2-二甲胺 基-1- (4_嗎啉基苯基）_丁酮心2·甲基小队甲硫基)苯基此 嗎啉基丙炫-1-酮、2,2，-雙（2,4-二氣苯基）_4,4，，5,5，-四笨基 -U’·聯咪唾、4,4’-雙（二乙胺基）二苯甲酮或2雀基苯並噻唾 較佳地，該光引發劑之含量為0.01至1〇重量％，更佳地〇1 至7重量％，從而提高穿透率並將曝光量減至最少。 通過一製程，本發明之負型光阻組合物可被用於形成圖 案，該製程包括：添加一溶劑，在基板上旋轉塗佈，使用一光 ❹ 罩照射紫外光以及藉由一鹼性顯影劑進行顯影。較佳地，添加 溶劑以使該負型光阻組合物之黏度為丨至兄厘泊。該溶劑可用 於溶解黏結樹脂、光敏劑及與彼等混合之其他添加劑，並得到 一具有優異塗佈雜及穿透率謂。以上述提及之目標之組合 物重量計，該溶劑之含量為10至94重量％。 考慮到與該黏結樹脂、光敏劑及其他化合物之相容性，根 據本發明之〉谷劑可為乙酸乙醋、乙酸丁醋、二乙二醇二甲鱗、 二乙二醇二甲基乙鱗、甲氧基丙酸甲酯、乙氧基丙酸乙醋 (EEP)、乳酸乙酯、丙二醇甲基醚乙酸酯(pGM£A)、丙二醇 甲醚、丙二醇丙醚、乙酸-2·甲氧乙醋、乙酸_2_乙氧乙醋、二 9 200944940 乙二醇乙酸甲酯、二乙二醇乙酸乙酯、丙酮、甲基異丁基酮、 環己酮、二甲基甲醯胺（DMF)、N,N_二甲基乙醢胺（DMAc)、 N-甲基-2-吡咯烷酮（nmp)、γ_丁内酯、二乙醚、乙二醇二 甲醚、二甘醇二甲醚(Diglyme)、四氫呋喃（ΤΗρ)、甲醇、乙 醇、丙醇、異丙醇、2-甲氧乙醇、2·乙氧乙醇、二乙二醇甲醚、 二乙二醇乙醚、二丙二醇甲醚、甲苯、二甲苯、己烷、庚烷或 辛烧’其可單獨或組合地使用。 以及’本發明之負型光阻組合物可進一步包括一用作助黏 劑之具有環氧基或胺基之石夕基化合物。該石夕基化合物可提高 ΙΤ^ (氧化銦錫）電極與該負型光阻組合物間之黏結強度並 提高硬化後之耐熱性。該含有環氧基或胺基之碎基化合物可為 (3-縮水甘油基氧基丙基）三曱氧基矽烷、（3_縮水甘油基氧 基丙基）三乙氧基矽烷、（3_縮水甘油基氧基丙基）甲基二曱 氧基矽烷、3,4-環氧基丁基三甲氧基矽烷、3,4·環氧基丁基三 乙氧基矽烷、2- (3,4-環氧基環己基）乙基三甲氧基矽烷、2_ (3,4-環氧基環己基）乙基三乙氧基石夕烷或胺基丙基三曱氧基 矽烧，其可單獨或組合地使用。 該矽基化合物之含量可根據需要適當地選擇，例如基於該 組合物之總重量計為0.001至5重量％。在矽基化合物之含量屬 於上述範圍之情況下，該光阻組合物在硬化後可顯示出優異的 黏結效果和耐熱性。 ，以及’在本發明之負型光阻組合物用於製造彩色濾光片之 情形下，該負型光阻組合物可進一步包括一通用彩色顏料漿。 該彩色顏之含量可根據需要適當地選擇，例於該組合 物之總重量計為2至40重量％。在該顏㈣之含量屬於上述範 圍之情形下，色純度及亮度性能均為優異。 200944940 以及’在本發明之負型光阻組合物用於樹脂型黑色矩陣 (BM)之情形下，該負型光阻組合物可進一步包括一通用碳 黑顏料漿。該碳黑顏料漿之含量可根據需要適當地選擇，例如 基於該組合物之總重量計為2至40重量％。在該碳黑顏料漿之 含量屬於上述範圍之情形下’可見光之遮蔽效應極優異並可良 好地保持顯影性能。 、 以及’本發明之負型光阻組合物可根據需要進一步包括一 可相容之添加劑，例如光敏劑、熱聚合抑制劑、消泡劑或平坦200944940 Ethoxyethyl ester, (methyl), decimine, N-methyl maleimine, N_ethyl maleimine, linoleimide, N-butyl mala Imine, N_cyclohexylmaleimine, ^pentylmaleimine, N-fresh base maleimide, phenylethylamine, 甲甲美=乙妇,乙乙oxyphenylethylene (Meth)acrylonitrile, hexyl ketone or vinyl acetate, which may be used singly or in combination. Preferably, the weight average molecular weight of the binder resin represented by the hybrid 丨 of the invention of the root county is I000 to 〇〇〇, the dispersibility is 1.0 to 1 〇. 〇, and more preferably, the weight average molecular weight thereof is 4,00 〇 to 1 (8),000, and the dispersion is 1.5 to 3.0. The binder resin of Chemical Formula 1 is a copolymer, and may be a random co-mix having a randomly-laid repeating unit, but the present invention is not limited thereto. In the negative resist composition of the present invention, the content of the binder resin can be appropriately controlled as needed, for example, from 3 to 50% by weight based on the total weight of the composition. In the negative-type photoresist composition of the present invention, the polyfunctional (meth)acryl-based monomer having at least one propylene group may be, for example, a monoester compound, and one by two per methyl group and the same. A product obtained by addition reaction of triglycidyl hydrazine acrylic acid or an addition reaction of phthalic anhydride with a product obtained by addition reaction of a novolac epoxy resin and (meth)acrylic acid An aldehyde-based epoxy acrylate resin, or a mixture thereof. The ester compound includes polyethylene glycol di(meth)acrylate having 2 to 20 ethylene oxide groups, ethylene glycol di(meth)acrylate, and polycondensation having 2 to 14 propylene oxide groups. Propylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trishydroxypropylpropane di(meth)acrylate, a product of addition reaction by diammonium A and diglycidyl ether acrylic acid , ethyl tris(meth)acrylate isocyanurate, 7 200944940 phthalic acid diester of p-hydroxyethyl methacrylate, by (meth)acrylic acid / 3-acetic acid Toluene diisocyanate g is a product of an addition reaction, trimethylolpropane tris(meth)acrylic acid vinegar, tetramethylol methane tetra(methyl)acrylic acid vinegar, isovaerythritol tris(methyl) ) vinegar vinegar, pentaerythritol tetrakis(methyl) propyl acrylate, diisopentaerythritol penta (methyl) propyl acetonate, diisopentaerythritol hexa (meth) acrylate S and Isoalcohol tris(meth)acrylic acid vinegar. The content of the polyfunctional (meth)glycol monomer may be appropriately controlled as needed, for example, 2 to 4% by weight based on the total weight of the composition, but the present invention is not limited thereto. When the content of the polyfunctional (meth)propionic acid monomer falls within the above-mentioned range, the film in the exposed portion remains good after exposure and display, and the degree of crosslinking of the film is maintained at a good level, so the film The performance and thermal stability are well maintained. A negative-type photoresist composition capable of maintaining film elasticity, chemical resistance and pattern stability can be prepared by appropriately controlling the composition ratio of the polyfunctional (?-based) propylene-based monomer residual resin according to the present invention. And the photoinitiator included in the negative resist composition according to the present invention may be a commonly used acetophenone derivative, benzophenone derivative or anthracene derivative. If the photoinitiator itself has a color, the transmittance will decrease. Preferably, the initiator has a suitable sensitivity and is colorless in the wavelength range used in the exposure process, resulting in high transmittance. Therefore, in the preparation of the negative-type photoresist composition of the present invention by crosslinking reaction using the polyfunctional (meth) propylene-based monomer, the wavelength of ultraviolet light used should be considered in order to appropriately select the light used for initiation. Agent. In the case where a mercury lamp is usually used, a photoinitiator which generates a radical at an ultraviolet wavelength of a mercury lamp of 31 Å to 45 Å is preferably used. - for example, the photoinitiator can be triphenylphosphine oxide, benzophenone, phenyl phenyl ketone, 1-hydroxy-1-benzoguanidinyl cyclohexane, benzyl dimethyl ketal, benzyl Base 200944940 monomethylamine (4-morphinyl-benzylidene)propane, 2-morphinyl_2_(4·methylsulfenyl)benzophenone, propyl ketone, 1-chloro -4-propyl poop brewing j, iso-diyl thioxanthone, diethyl thioxanthone, ethyl hydrazine, 4-benzylidene _4-methyl diphenyl sulfide, benzamidine Butyl ether, 2-hydroxy-2-benzhydrylpropane, 2-hydrazino-2-(4-isopropyl)benzimidyl propane, 4-butylbenzylidene trichloromethane, Phenoxybenzoinyl methylene chloride, methyl benzhydrazinic acid, hydrazine, 7-bis(9_3 acridinyl) Geng, 9-n-butyl-3,6-bis (2-morphinyl) Isobutyryl) σ 哇, methyl _4,6 bis (difluoromethyl)-s-triazine, 2-phenyl _4,6 bis (trichloromethyl) ❹ s Qinyl-4,6-bis(dichloromethyl)-s-triterpene, 2·benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone heart 2·A Base group methylthio)phenyl this morpholinyl propan-1-one, 2,2,-bis (2,4-di Phenyl)_4,4,5,5,-tetraphenyl-U'·Limi, 4,4'-bis(diethylamino)benzophenone or 2 fenyl benzothiophene Preferably, the photoinitiator is present in an amount of from 0.01 to 1% by weight, more preferably from 1 to 7% by weight, thereby increasing the penetration rate and minimizing the amount of exposure. The negative photoresist composition of the present invention can be used to form a pattern by a process comprising: adding a solvent, spin coating on a substrate, irradiating ultraviolet light with a light mask, and developing by an alkali The agent is developed. Preferably, a solvent is added to make the negative photoresist composition have a viscosity of from 丨 to 厘 centipoise. The solvent can be used to dissolve the binder resin, the photosensitizer, and other additives mixed with them, and to obtain an excellent coating and penetration rate. The solvent is contained in an amount of 10 to 94% by weight based on the weight of the composition of the above-mentioned target. In view of compatibility with the binder resin, photosensitizer and other compounds, the gluten agent according to the present invention may be ethyl acetate, butyl acetate, diethylene glycol dimethyl scale, diethylene glycol dimethyl glycol. Scale, methyl methoxypropionate, ethyl ethoxypropionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (pGM£A), propylene glycol methyl ether, propylene glycol propyl ether, acetic acid-2 Methoxyethyl vinegar, acetic acid _2 _ ethoxy ethoxy vinegar, two 9 200944940 ethylene glycol methyl acetate, ethyl diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamidine Amine (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (nmp), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol Diglyme, tetrahydrofuran (ΤΗρ), methanol, ethanol, propanol, isopropanol, 2-methoxyethanol, 2. ethoxyethanol, diethylene glycol methyl ether, diethylene glycol diethyl ether, dipropylene glycol Methyl ether, toluene, xylene, hexane, heptane or octane can be used singly or in combination. And the negative photoresist composition of the present invention may further comprise a sulfonium compound having an epoxy group or an amine group as an adhesion promoter. The Schiff base compound can improve the bonding strength between the ΙΤ^ (indium tin oxide) electrode and the negative-type photoresist composition and improve the heat resistance after hardening. The base compound containing an epoxy group or an amine group may be (3-glycidyloxypropyl)trimethoxy decane, (3-glycidyloxypropyl)triethoxydecane, (3) _ glycidyl propyl propyl) methyl decyloxy decane, 3,4-epoxy butyl trimethoxy decane, 3,4 epoxy butyl triethoxy decane, 2- (3 , 4-epoxycyclohexyl)ethyltrimethoxydecane, 2_(3,4-epoxycyclohexyl)ethyltriethoxy oxane or aminopropyltrimethoxy oxime, which Used singly or in combination. The content of the mercapto compound can be appropriately selected as needed, for example, from 0.001 to 5% by weight based on the total weight of the composition. In the case where the content of the mercapto compound is in the above range, the photoresist composition exhibits an excellent bonding effect and heat resistance after hardening. And in the case where the negative photoresist composition of the present invention is used to produce a color filter, the negative photoresist composition may further comprise a universal color pigment paste. The content of the colored pigment can be appropriately selected as needed, and is, for example, 2 to 40% by weight based on the total weight of the composition. In the case where the content of the pigment (4) is in the above range, color purity and brightness performance are excellent. 200944940 and In the case where the negative photoresist composition of the present invention is used in a resin type black matrix (BM), the negative photoresist composition may further comprise a general carbon black pigment paste. The content of the carbon black pigment paste can be appropriately selected as needed, for example, 2 to 40% by weight based on the total weight of the composition. In the case where the content of the carbon black pigment paste falls within the above range, the visible light shielding effect is extremely excellent and the development performance can be favorably maintained. And the negative photoresist composition of the present invention may further comprise a compatible additive as needed, such as a photosensitizer, a thermal polymerization inhibitor, an antifoaming agent or a flat
劑0 在下文中，將通過實例及比較實例詳細說明本發明。應瞭 解，由於在本發明之精神和範圍内所進行之各種變化和修改可 通過該詳細說明而為熟習此項技術者顯而易見，因此在說明本 發明之較佳實施例時可僅藉由舉例說明方式給出詳細說明及 特定實例。 ° 實例1 將150毫升丙二醇甲基醚乙酸酯（PGMEA)放入—配備紫 外光遮蔽膜及攪拌器之混合室中。根據下表丨中所示之組分及 含量順次加入樹脂黏結劑、多官能基（甲基）丙烯基單體及光 引發劑。以及，加入0.1重量％2FC-430(—種3M公司製造之平 坦劑）。然後在室溫下製備並攪拌負型光阻組合物。接著，加 入PGMEA從而控制該組合物之黏度至18厘泊。 實例2至9 根據下表1之組分及含量、按照實例1中所述之相同方式製 備負型光阻組合物。 表1 實例具有化學式1之黏結樹脂（重量 %) 多官能基（曱基)丙 烯基單體（重量％) 光引發劑 (重量％) 溶劑 11 200944940Agent 0 Hereinafter, the present invention will be described in detail by way of examples and comparative examples. It will be apparent to those skilled in the art that the present invention may be <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The method gives a detailed description and a specific example. ° Example 1 150 ml of propylene glycol methyl ether acetate (PGMEA) was placed in a mixing chamber equipped with an ultraviolet light shielding film and a stirrer. The resin binder, the polyfunctional (meth) propylene monomer, and the photoinitiator are sequentially added according to the components and contents shown in the following table. And, 0.1% by weight of 2FC-430 (a flat agent manufactured by 3M Company) was added. The negative photoresist composition was then prepared and stirred at room temperature. Next, PGMEA was added to control the viscosity of the composition to 18 cps. Examples 2 to 9 A negative photoresist composition was prepared in the same manner as described in Example 1 according to the components and contents of Table 1 below. Table 1 Examples of a binder resin of Chemical Formula 1 (% by weight) Polyfunctional (fluorenyl) propenyl monomer (% by weight) Photoinitiator (% by weight) Solvent 11 200944940
1 A: 3,4-環氧基甲基丙烯酸丁酯 B:N-甲基馬來醯胺酸 C:苯乙烯 x=0.3 5 y=0.3，z=0.4 ( 30 ) 二異戊四醇六丙稀 酸酯（20) 2-甲基-1-[(4-甲 硫基)笨基]-2-嗎 啉基丙烷-1-酮（ 1) PGME Α(至1 00) 2 A:曱基丙豨酸縮水甘油S旨 B:N-乙基馬來醯胺酸 C:曱基丙烯酸異冰片酯 χ=0·3，y=0.3，z=0.4 (30) 一種由雙酚Α與二 縮水甘油鰱丙烯酸 進行加成反應之產 物（25) 2-巯基笨並噻唑 (0.5) 3 A: 2,3-環氧基甲基丙烯酸環己酯 B:N-苯基馬來醯胺酸 C:曱基丙烯酸甲酯 x=0.25 5 y=0.2 > z=0.6 (30) 二乙二醇二丙烯酸 m (3〇) 4-苯甲醯基-4-甲 基二苯基硫化物 (3) 4 A:甲基丙烯酸縮水甘油酯 B:N-環己基馬來醯胺酸 C:環己基丙烯酸酯 x=0.4，y=0.3，z=0.3 (30) 四經甲基甲烧四甲 基丙烯酸酯(15) 2-嗎啉基-2- (4-甲基巯基）苯甲 醯基丙烷（1.5) 5 A:曱基丙稀酸縮水甘油醋 B:N-甲基馬來醯胺酸甲酯 C:馬來醯亞胺 x=0.4，y=0.3，ζ=0·3 (30) 異戊四醇三丙烯酸 酯(20) 1-苄基-1-二甲胺 基-1- (4-嗎啉基-苯甲醯基）丙烷 (1) 6 A: 3,4-環氧基丙烯酸丁酯 Β: Ν- 乙基 -2,3-二甲基馬來醯胺酸 C:苯乙烯 x=0.3，y=0.25，ζ=0·45 (30) 三羥甲基丙烷三丙 烯酸酯（7) 2-甲基-4,6-雙（ 三氣甲基）-s-三 嗪⑴ 7 Α:丙稀酸縮水甘油S旨 B:N-二甲基馬來醯胺酸 C:乙醯氧基苯乙烯 χ=0·4，}^=0·4，ζ=0·2 (30) 四經甲基甲烧四丙 烯酸酯（15) 2-萘基-4,6-雙（ 三氣甲基）-s-三 嗪（1.5) 8 A: 3,4-環氧基甲基丙烯酸環己酯 -甲基丙烯酸β-羥 2-嗎啉基-2- (4- 12 200944940 B:N-癸基馬來醯胺酸 C:丙烯酸金剛烷酯 x=0.4，y=0.15，ζ=0·45 (30) 乙酯之鄰笨二甲酸 二酯（10) 甲基毓基）笨甲 醢基丙烷（1) 9 Α:曱基丙稀酸縮水甘油醋 B: N- (p-羥苯基）馬來醯胺酸甲醋 C:乙酸乙烯酯 x=0_15，y=0.45 ’ z=0.4 (30) 三羥甲基丙烷二丙 烯酸酯（10)與二 異戊四醇六丙烯酸 酯 異丙基噻噸酮（ 4) *具有化學式1之黏結樹脂之重均分子詈為9000至10,_，多, 令散性為2.1。 -----—^ 比較實例1及會你丨91 A: 3,4-epoxy butyl methacrylate B: N-methyl maleic acid C: styrene x = 0.3 5 y = 0.3, z = 0.4 ( 30 ) diisopentaerythritol Acrylate (20) 2-methyl-1-[(4-methylthio)phenyl]-2-morpholinylpropan-1-one ( 1) PGME Α (to 1 00) 2 A: 曱Glycidyl glycidyl S. B: N-ethyl maleic acid C: isobornyl mercaptoate χ = 0.3, y = 0.3, z = 0.4 (30) A bisphenol hydrazine and two The product of the addition reaction of glycidol and acrylic acid (25) 2-mercaptobenzothiazole (0.5) 3 A: 2,3-epoxy methacrylic acid cyclohexyl ester B: N-phenyl maleic acid C Methyl methacrylate x=0.25 5 y=0.2 > z=0.6 (30) Diethylene glycol diacrylate m (3〇) 4-Benzylmercapto-4-methyldiphenyl sulfide (3 4 A: glycidyl methacrylate B: N-cyclohexyl maleic acid C: cyclohexyl acrylate x = 0.4, y = 0.3, z = 0.3 (30) tetramethylpyrenetetramethyl Acrylate (15) 2-morpholinyl-2-(4-methylindolyl)benzimidylpropane (1.5) 5 A: mercapto acrylic acid glycidol vinegar B: N-methyl maleic acid Methyl ester C: maleimide x=0.4, y=0.3, ζ=0·3 (30) Isopentanol triacrylate (20) 1-benzyl-1-dimethylamino-1-(4-morpholinyl-benzylidene)propane (1) 6 A: 3,4- Butyl butyl acrylate: Ν-ethyl-2,3-dimethylmaleamic acid C: styrene x=0.3, y=0.25, ζ=0.45 (30) Trimethylolpropane Triacrylate (7) 2-methyl-4,6-bis(trimethylmethyl)-s-triazine (1) 7 Α: glycidyl acrylate S B: N-dimethylmaleamic acid C: ethoxylated styrene χ =0,4,}^=0·4, ζ=0·2 (30) tetramethyl methacrylate tetraacrylate (15) 2-naphthyl-4,6- Bis(trimethylmethyl)-s-triazine (1.5) 8 A: 3,4-epoxy methacrylate cyclohexyl- methacrylate β-hydroxy 2-morpholinyl-2- (4- 12 200944940 B: N-decylmaline decanoic acid C: adamantyl acrylate x=0.4, y=0.15, ζ=0.45 (30) Ethyl phthalate diester (10) methyl fluorenyl ) 笨 醢 醢 丙烷 ( (1) 9 Α: mercapto acrylic acid glycidol vinegar B: N- (p-hydroxyphenyl) maleic acid methyl vinegar C: vinyl acetate x = 0_15, y = 0.45 ' z=0.4 (30) Trimethylolpropane diacrylate (10) and diisopentaerythritol hexaacrylate Thioxanthone (4) having a chemical formula weight * resin bonding of an average molecular curse of 9000-10, _, multiple, so that dispersibility is 2.1. ------^ Compare example 1 and will you 丨9
根據下表2所示之組分及含量、按照實例丨中所述之相同方 式製備負型光阻組合物，不同之處在於：使用下述化學式3表 示之黏結樹脂代替實例丨中之黏結樹脂。 【化學式3】A negative photoresist composition was prepared in the same manner as described in the following Table 2 in the same manner as described in the following Table 2, except that the binder resin represented by the following Chemical Formula 3 was used instead of the binder resin in the example. . [Chemical Formula 3]
【表2】 比較實 例 具有化學式3之黏結 樹脂（30重量％ ) 多官能基（甲 基）丙烯基單體 (重量％) 光引發劑 (重量％) 添加劑 (重量％) 溶劑 1 —-------- 1=0.3， m=0.5， n=0.2 二異戊四醇六 丙烯酸酯（20) 2-嗎淋基 -2-(4-甲基 巯基）苯曱 醯基丙烷 FC-430(0.1) PGMEA (至 100) 2 1=0.3， m=0.4, n=0.3 ------ 具有化學式3之赌触之重均分子量奶，麵至1()，_，彡分紐為η。 以及PGMEAS 丙二醇 f 細 13 200944940 5式驗實例 比較實例之㈣細#實施例和 :強度、料衫.、賴/及： 估。所得結果如下表3和表4所示。 進仃汗 (1)黏結強度 ❹ 使用-旋轉塗佈機將負型光阻組合物塗敷於 二(^預^丨分鐘，在365奈米之紫外光下曝光15秒鐘: i入3G分鐘從而形成—光_。然後將該光阻膜 基板。將黏結帶黏貼至該樣品上，絲將其與 露= =：祕；Γ侧格健概絲上之_下，J為ί 結強度優良，，否則為“差”。 (2)紫外光穿透率 。使用-旋轉塗佈機將負型光阻組合物塗敷於一基板上，在 :巧預烘倍’藉由238%ΤΜΑΗ溶液嘴射顯影_ 里接者使用絲子（DI)水沖洗6G秒鐘，賴縮空氣吹掃， 然後在24G C下後烘培3G分鐘，從而形成—3微米之紐膜。使❹ 紫外光穿透該光阻膜。測試波長4〇〇奈米下之穿透率。 (3)殘膜率 。將負型光阻組合物旋轉塗佈於一基板上，接著測試在2〇〇 C下預烘焙30分鐘後之第一厚度與在24〇。(：下再烘焙丨個小時 後之第二厚度的比率（％)。 (4)圖案形成 將具有負型光阻組合物之矽晶圓沿孔圖案之軸向進行切 割，然後利用電子顯微鏡在該圖案之截面方向進行觀察。在圖 案之側壁與該基板間的角度為55。或大於55。以及膜厚度不減 14 200944940 小之情形下，認為該負型光阻組合物之圖案形成為“優良”， 而在膜厚度減小之情形下，則認為其圖案形成為“膜厚度減 ρ :表3】 實例 黏結強度 紫外光穿透率 殘膜率 圖案形成 (400奈米）(％) (%) 1 -- 優良 97 96 優良 2 — 優良 98 95 優良 一 3 優良 98 97 4 優良 98 96 優良 5 優良 97 95 優良 6 優良 97 96 --- 7 優良 98 97 優良 8 — 優良 96 96 ------ 優良 9 優良 95 98 ·— — 優良 r L I3L 1[Table 2] Comparative Example A bonding resin of Chemical Formula 3 (30% by weight) Polyfunctional (meth)acryl-based monomer (% by weight) Photoinitiator (% by weight) Additive (% by weight) Solvent 1 —--- ----- 1=0.3, m=0.5, n=0.2 Diisopentaerythritol hexaacrylate (20) 2-M-Pentyl-2-(4-methylindenyl)phenylhydrazine propane FC-430 (0.1) PGMEA (to 100) 2 1=0.3, m=0.4, n=0.3 ------ The weight average molecular weight of the chemical formula 3, face to 1 (), _, 彡η. And PGMEAS propylene glycol f fine 13 200944940 5 test examples Comparative examples (4) fine #Examples and: strength, shirt. Lai / and: Estimate. The results obtained are shown in Tables 3 and 4 below. Into the sweat (1) Bonding strength 涂敷 Apply the negative photoresist composition to the second using a spin coater, and expose it to 365 nm for 15 seconds: i into 3G minutes. Thus forming a light _. Then the photoresist film substrate is adhered to the sample, the wire is attached to the lacquer = : 秘 Γ Γ Γ Γ Γ Γ Γ , , , , , , , , , , , , otherwise "poor". (2) UV transmittance. The negative photoresist composition is applied to a substrate using a spin coater. Mouth development _ The lining is rinsed with silk (DI) water for 6G seconds, then immersed in air and then baked at 24G C for 3G minutes to form a 3 micron film. Through the photoresist film, the transmittance at a wavelength of 4 nanometers is tested. (3) Residual film rate. The negative photoresist composition is spin-coated on a substrate, and then tested at 2 〇〇C. The first thickness after baking for 30 minutes is at a ratio (%) at 24 〇. (: second thickness after baking for another hour.) (4) Pattern formation will have a negative resist composition The circle is cut along the axial direction of the hole pattern, and then observed in the cross-sectional direction of the pattern by an electron microscope. The angle between the side wall of the pattern and the substrate is 55. or greater than 55. The film thickness is not reduced by 14 200944940 Next, it is considered that the pattern of the negative resist composition is formed as "excellent", and in the case where the film thickness is reduced, the pattern is considered to be "film thickness minus ρ: Table 3] Example Bond Strength Ultraviolet Light Penetration Rate residual film rate pattern formation (400 nm) (%) (%) 1 -- Excellent 97 96 Excellent 2 - Excellent 98 95 Excellent one 3 Excellent 98 97 4 Excellent 98 96 Excellent 5 Excellent 97 95 Excellent 6 Excellent 97 96 - -- 7 Excellent 98 97 Excellent 8 — Excellent 96 96 ------ Excellent 9 Excellent 95 98 · — Excellent r L I3L 1
_ 膜厚度減小 如上it結麵示，根據本發紅祕㈣ :==;型光阻組合物不同’其具有優異的= =屬和無機材料的黏著力、紫外光穿透率、殘辭以及圖案穩 【圖式簡單說明】 盔 【主要元件符號說明】 盔 15_ The film thickness is reduced as shown in the figure below, according to the red hair (4): ==; type resist composition is different 'its have excellent = = genus and inorganic material adhesion, UV transmittance, residual words And the pattern is stable [simple description of the figure] helmet [main symbol description] helmet 15
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