TWI392909B - Organic-inorganic hybrid photosensitive resin composition and liquid crystal display comprising cured body thereof - Google Patents
Organic-inorganic hybrid photosensitive resin composition and liquid crystal display comprising cured body thereof Download PDFInfo
- Publication number
- TWI392909B TWI392909B TW097126860A TW97126860A TWI392909B TW I392909 B TWI392909 B TW I392909B TW 097126860 A TW097126860 A TW 097126860A TW 97126860 A TW97126860 A TW 97126860A TW I392909 B TWI392909 B TW I392909B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- methacrylate
- weight
- acrylate
- resin composition
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明關於鈍化膜用的有機-無機混成感光性樹脂組成物以及含其硬化體的液晶顯示器(LCD),且更詳細地關於一種感光性樹脂組成物,其具有低介電常數及優異的黏著性、耐熱性、絕緣性、平坦性及耐化學性,而因此適用作為用於形成LCD的影像之材料,而且其在形成LCD的鈍化有機絕緣膜後係表現低介電常數及優異的抗濕性、黏著性及耐熱性,而因此適合充當有機絕緣膜,再者其係被利用當作罩面層用的光阻樹脂、黑色矩陣用的光阻樹脂、柱狀間隔物用的光阻樹脂、或彩色濾光片用的光阻樹脂,而因此增進耐熱性、黏著性等。The present invention relates to an organic-inorganic hybrid photosensitive resin composition for a passivation film and a liquid crystal display (LCD) containing the same, and more particularly to a photosensitive resin composition having a low dielectric constant and excellent adhesion. Properties, heat resistance, insulation, flatness, and chemical resistance, and thus are suitable as materials for forming an image of an LCD, and exhibit low dielectric constant and excellent moisture resistance after forming a passivated organic insulating film of an LCD. It is suitable for use as an organic insulating film, and is also used as a photoresist resin for an overcoat layer, a photoresist resin for a black matrix, and a photoresist resin for a column spacer. Or a photoresist resin for a color filter, thereby improving heat resistance, adhesion, and the like.
通常,主要用於裝置的有機絕緣體係由SiO2 所製成。理由為Si具有良好的絕緣效率且主要用基板,其本身有利於薄膜的形成。然而,Si具有非晶形結構及3.9之等級的高介電常數,因此性能上係不適合用作為最理想的低介電常數有機絕緣體。Usually, the organic insulating system mainly used for the device is made of SiO 2 . The reason is that Si has a good insulating efficiency and mainly uses a substrate, which itself contributes to the formation of a film. However, Si has an amorphous structure and a high dielectric constant of 3.9 grade, and thus is not suitable for use as an optimum low dielectric constant organic insulator.
鈍化膜用的有機絕緣體必須具有低介電常數,以便減少電荷遷移率,即使在低的厚度下,因此增加絕緣性及開/關比,藉以增進TFT驅動性。The organic insulator for the passivation film must have a low dielectric constant in order to reduce the charge mobility, and even at a low thickness, the insulation and the on/off ratio are increased, thereby enhancing the TFT driving property.
本發明的鈍化有機絕緣膜係一種丙烯酸有機絕緣膜,具有約280℃的低耐熱性。為了達成所欲的可靠性,當確保 300℃或更高的耐熱性時,絕緣膜係被視為穩定的。然而,習知的SiO2 及丙烯酸絕緣體係不利的,因為增加成本和介電常數,及減少耐熱性,抗濕性和黏著性。The passivated organic insulating film of the present invention is an acrylic organic insulating film having a low heat resistance of about 280 °C. In order to achieve the desired reliability, the insulating film is considered to be stable when heat resistance of 300 ° C or higher is ensured. However, conventional SiO 2 and acrylic insulating systems are disadvantageous because of increased cost and dielectric constant, and reduced heat resistance, moisture resistance and adhesion.
因此,本發明已經注意到在相關技藝中所發生的上述問題,而且本發明提供一種有機-無機混成感光性樹脂組成物,其具有低介電常數及優異的黏著性、耐熱性、絕緣性、平坦性及耐化學性,而因此能用當作一種用於形成LCD之影像的材料,再者其在形成LCD的有機-無機混成鈍化絕緣膜後係表現低介電常數及優異的抗濕性、黏著性及耐熱性,而因此非常適合充當鈍化絕緣膜,而且本發明亦提供一種含有其硬化體的LCD。Accordingly, the present invention has been made aware of the above problems occurring in the related art, and the present invention provides an organic-inorganic hybrid photosensitive resin composition having a low dielectric constant and excellent adhesion, heat resistance, insulation, Flatness and chemical resistance, so it can be used as a material for forming an image of an LCD, and further exhibits a low dielectric constant and excellent moisture resistance after forming an organic-inorganic hybrid passivation insulating film of an LCD. It is excellent in adhesion and heat resistance, and thus is very suitable as a passivation insulating film, and the present invention also provides an LCD including a hardened body thereof.
依照本發明,一種有機-無機混成感光性樹脂組成物包含:(a)膠態無機溶膠,(b)由(i)不飽和羧酸、不飽和羧酸酐或其混合物與(ii)至少一種丙烯酸不飽和化合物之共聚合反應所產生丙烯酸共聚物,(c)光引發劑,(d)具有乙烯性不飽和鍵的多官能單體,(e)含有環氧基或胺基的矽系化合物,及(f)溶劑。而且,提供一種含其硬化體的LCD。According to the present invention, an organic-inorganic hybrid photosensitive resin composition comprises: (a) a colloidal inorganic sol, (b) from (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof and (ii) at least one acrylic acid An acrylic copolymer produced by copolymerization of an unsaturated compound, (c) a photoinitiator, (d) a polyfunctional monomer having an ethylenically unsaturated bond, (e) an anthracene compound containing an epoxy group or an amine group, And (f) a solvent. Moreover, an LCD including a hardened body thereof is provided.
具體地,(a)膠態無機溶膠之形成係藉由添加膠態無機奈米粒子與1~120重量份的有機矽烷,以便有機矽烷與無機奈米粒子的表面反應,去除水,然後添加有機溶劑,因 此使得反應介質成為疏水性。膠態無機奈米粒子較佳為由水分散性膠體無機材料構成,其包含至少一種選自於矽石,氧化鋁、二氧化鈦、氧化鋯、氧化錫、氧化鋅、能與有機矽烷反應的有機材料、及經矽石所表面改質的無機材料。Specifically, (a) the colloidal inorganic sol is formed by adding colloidal inorganic nanoparticles and 1 to 120 parts by weight of organodecane so that the organic decane reacts with the surface of the inorganic nanoparticles to remove water and then add organic Solvent This makes the reaction medium hydrophobic. The colloidal inorganic nanoparticles are preferably composed of a water-dispersible colloidal inorganic material comprising at least one organic material selected from the group consisting of vermiculite, alumina, titania, zirconia, tin oxide, zinc oxide, and organic decane. And inorganic materials modified by the surface of meteorites.
因此,該方法包括添加經水分散的膠態無機材料與有機矽烷,去除水,及添加有機溶劑,可一次或以預定的時間間隔重複地進行。Therefore, the method includes adding a water-dispersed colloidal inorganic material and an organic decane, removing water, and adding an organic solvent, which can be repeatedly performed once or at predetermined time intervals.
有機矽烷係由下式所代表:R1 0~3 Si(OR2 )1~4 ,其中R1 係至少一種選自於烷基、苯基、氟碳烷基、丙烯醯基、甲基丙烯醯基、烯丙基、乙烯基及環氧基,R2 係至少一種選自於甲基、乙基、異丙基、正丙基及正丁基,且OR2 係烷氧基、醋酸酯基或肟基 膠態無機溶膠的用量較佳為1~95重量份。The organic decane is represented by the following formula: R 1 0~3 Si(OR 2 ) 1~4 , wherein at least one of R 1 is selected from the group consisting of alkyl, phenyl, fluorocarbon alkyl, acryl fluorenyl, methacryl acyl, an allyl group, a vinyl group and an epoxy group, R 2 Department least one selected from methyl, ethyl, isopropyl, n-propyl and n-butyl group, and an alkoxy group OR 2 based, acetate The amount of the base or sulfhydryl colloidal inorganic sol is preferably from 1 to 95 parts by weight.
再者,樹脂組成物包含:(b)100重量份的丙烯酸共聚物,其係由共聚合(i)5~40重量份的不飽和羧酸、不飽和羧酸酐或其混合物與(ii)5~95重量份的至少一種丙烯酸不飽和化合物而獲得;(c)0.001~30重量份的光引發劑;(d)10~100重量份的具有乙烯性不飽和鍵的多官能單體;(e)0.0001~5重量份的含有環氧基或胺基的矽系化合物;及(f)溶劑,其用量係使得感光性樹脂組成物的固體含量成為10~50重量份。Further, the resin composition comprises: (b) 100 parts by weight of an acrylic copolymer which is copolymerized (i) 5 to 40 parts by weight of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof and (ii) 5 ~95 parts by weight of at least one acrylic acid unsaturated compound; (c) 0.001 to 30 parts by weight of a photoinitiator; (d) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond; 0.0001 to 5 parts by weight of an anthracene compound containing an epoxy group or an amine group; and (f) a solvent in an amount of 10 to 50 parts by weight based on the solid content of the photosensitive resin composition.
(a)膠態無機奈米粒子具有1~100nm的大小之球形或100~1000nm的大小之纖維形。當膠態無機奈米粒子的表面 經具有反應基的有機矽烷所處理時,無機奈米粒子係穩定地分散在有機溶劑中,因此表現高的穩定性且以分子程度化學地鍵結它們與有機樹脂。(a) Colloidal inorganic nanoparticles have a spherical shape of 1 to 100 nm or a fiber shape of a size of 100 to 1000 nm. When the surface of colloidal inorganic nanoparticles When treated with an organic decane having a reactive group, the inorganic nanoparticles are stably dispersed in an organic solvent, thus exhibiting high stability and chemically bonding them to the organic resin at a molecular level.
(b)丙烯酸共聚物係可藉由使單體在溶劑及聚合引發劑的存在下進行自由基反應而製備,該單體包含(i)不飽和羧酸、不飽和羧酸酐或其混合物,及(ii)丙烯酸不飽和化合物。(b) an acrylic copolymer can be prepared by subjecting a monomer to a radical reaction in the presence of a solvent and a polymerization initiator, the monomer comprising (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof, and (ii) an acrylic unsaturated compound.
於本發明中,(b)(i)不飽和羧酸、不飽和羧酸酐或其混合物的例子包括不飽和一元羧酸,如丙烯酸、甲基丙烯酸等;不飽和二羧酸,如馬來酸,富馬酸、檸康酸、仲康酸、伊康酸等;及其不飽和二羧酸酐,彼可單獨使用或以其二或多種的組合使用。為了在用作為顯影劑的鹼性水溶液中實現所欲的共聚合反應性及溶解性,特別可有用的是丙烯酸、甲基丙烯酸或馬來酸酐。In the present invention, examples of (b) (i) an unsaturated carboxylic acid, an unsaturated carboxylic anhydride or a mixture thereof include an unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or the like; and an unsaturated dicarboxylic acid such as maleic acid. , fumaric acid, citraconic acid, sec-conic acid, itaconic acid, etc.; and its unsaturated dicarboxylic anhydride, which may be used singly or in combination of two or more thereof. Acrylic acid, methacrylic acid or maleic anhydride is particularly useful for achieving desired copolymerization reactivity and solubility in an aqueous alkaline solution used as a developer.
以單體的總重量為基準,不飽和羧酸、不飽和羧酸酐或其混合物的用量為5~40重量份。若其量少於5重量份,則此成分難以溶解在鹼性水溶液中。相反地,若量超過40重量份,則此成分在鹼性水溶液中的溶解性過高。The unsaturated carboxylic acid, the unsaturated carboxylic anhydride or a mixture thereof is used in an amount of 5 to 40 parts by weight based on the total weight of the monomers. If the amount is less than 5 parts by weight, the component is difficult to dissolve in an alkaline aqueous solution. On the contrary, if the amount exceeds 40 parts by weight, the solubility of this component in an aqueous alkaline solution is too high.
於本發明中,(b)(ii)丙烯酸不飽和化合物包括含環氧基的不飽和化合物及烯烴不飽和化合物。In the present invention, (b) (ii) the acrylic unsaturated compound includes an epoxy group-containing unsaturated compound and an olefin unsaturated compound.
含環氧基的不飽和化合物之例子包括丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油基酯、α-正丁基丙烯酸縮水甘油酯、丙烯酸β-甲基縮水甘油酯、甲基丙烯酸β-甲基縮水甘 油酯、丙烯酸β-乙基縮水甘油酯、甲基丙烯酸β-乙基縮水甘油酯、丙烯酸3,4-環氧丁酯、甲基丙烯酸3,4-環氧丁酯、丙烯酸6,7-環氧庚酯、甲基丙烯酸6,7-環氧庚酯、α-乙基丙烯酸6,7-環氧庚基酯、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、及對乙烯基苄基縮水甘油基醚。此化合物可單獨使用或以其二或多種的組合使用。Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α-n-butyl acrylate shrinkage. Glyceryl ester, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate Oil ester, β-ethyl glycidyl acrylate, β-ethyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylic acid 6,7- Epoxyheptyl ester, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl Ether, and p-vinylbenzyl glycidyl ether. This compound may be used singly or in combination of two or more kinds thereof.
作為含環氧基的不飽和化合物,為了實現所欲的共聚合反應性及增加所生成的圖案之耐熱性,特別適用的是甲基丙烯酸縮水甘油酯、甲基丙烯酸β-甲基縮水甘油酯、甲基丙烯酸6,7-環氧庚酯,鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、或對乙烯基苄基縮水甘油基醚。As the epoxy group-containing unsaturated compound, in order to achieve desired copolymerization reactivity and increase the heat resistance of the resulting pattern, glycidyl methacrylate, β-methyl glycidyl methacrylate is particularly suitable. 6,6-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, or p-vinylbenzyl glycidyl ether.
以單體的總重量為基準,含環氧基的不飽和化合物之用量為10~70重量份,且較佳為20~60重量份。若其量少於10重量份,則所生成的圖案之耐熱性低。相反地,若量超過70重量份,則共聚物的儲存穩定性係不宜地低。The epoxy group-containing unsaturated compound is used in an amount of 10 to 70 parts by weight, based on the total weight of the monomers, and preferably 20 to 60 parts by weight. If the amount is less than 10 parts by weight, the heat resistance of the resulting pattern is low. On the contrary, if the amount exceeds 70 parts by weight, the storage stability of the copolymer is undesirably low.
再者,烯烴不飽和化合物的例子包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、丙烯酸甲酯、丙烯酸異丙酯、甲基丙烯酸環己酯、甲基丙烯酸2-甲基環己酯、丙烯酸二環戊烯酯、丙烯酸二環戊酯、甲基丙烯酸二環戊烯酯、甲基丙烯酸二環戊酯、丙烯酸1-金剛烷酯、甲基丙烯酸1-金剛烷酯、甲基丙烯酸二環戊氧基乙酯、甲基丙烯酸異冰片酯、丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸二環戊氧基乙酯、丙烯酸異冰片酯、甲基丙烯酸苯酯、丙烯酸 苯酯、丙烯酸苄酯、甲基丙烯酸2-羥乙酯、苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、1,3-丁二烯、異戊二烯、及2,3-二甲基-1,3-丁二烯。此化合物可單獨使用或以其二或多種的組合使用。Further, examples of the olefin unsaturated compound include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, third butyl methacrylate, methyl acrylate, acrylic acid. Isopropyl ester, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentyl methacrylate Ester, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, Dicyclopentyloxyethyl acrylate, isobornyl acrylate, phenyl methacrylate, acrylic acid Phenyl ester, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1, 3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. This compound may be used singly or in combination of two or more kinds thereof.
作為烯烴不飽和化合物,為了達成所欲的共聚合反應性及在用作為顯影劑的鹼性水溶液中之溶解性,特別適用的是苯乙烯、甲基丙烯酸二環戊基甲酯或對甲氧基苯乙烯。As the olefin unsaturated compound, in order to achieve desired copolymerization reactivity and solubility in an aqueous alkaline solution used as a developer, styrene, dicyclopentylmethyl methacrylate or p-methoxy is particularly suitable. Styrene.
以單體的總重量為基準,烯烴不飽和化合物的用量為10~70重量份,且較佳為20~50重量份。當其用量落於上述範圍內,則可避免關於丙烯酸共聚物之低儲存穩定性及在用作為顯影劑的鹼性水溶液中之溶解性的不可能性之問題。The olefin unsaturated compound is used in an amount of 10 to 70 parts by weight, based on the total weight of the monomers, and preferably 20 to 50 parts by weight. When the amount thereof falls within the above range, the problem of the low storage stability of the acrylic copolymer and the impossibility of solubility in an aqueous alkaline solution as a developer can be avoided.
用於使上述單體聚合成丙烯酸共聚物的溶劑之例子包括醚類,如甲醇、四氫呋喃、乙二醇單甲基醚、乙二醇單乙基醚、甲基溶纖劑醋酸酯、乙基溶纖劑醋酸酯、二乙二醇單甲基醚,二乙二醇單乙基醚,乙二醇二甲基醚、乙二醇二乙基醚、乙二醇甲基乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇丙基醚、丙二醇丁基醚、丙二醇甲基醚醋酸酯、丙二醇乙基醚醋酸酯、丙二醇丙基醚醋酸酯、丙二醇丁基醚醋酸酯、丙二醇甲基乙基丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯、甲苯、二甲苯、甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、醋酸甲酯、醋酸乙酯、醋酸丙酯、醋酸丁酯、2- 羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基醋酸甲酯、羥基醋酸乙酯、羥基醋酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸丙酯、乙氧基醋酸丁酯、丙氧基醋酸甲酯、丙氧基醋酸乙酯、丙氧基醋酸丙酯、丙氧基醋酸丁酯、丁氧基醋酸甲酯、丁氧基醋酸乙酯、丁氧基醋酸丙酯、丁氧基醋酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、及3-丁氧基丙酸丁酯。此化合物可單獨使用或以其二或多種的組合使用。Examples of the solvent for polymerizing the above monomer into an acrylic copolymer include ethers such as methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl Cellulolytic acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol Methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxyl -4-methyl-2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 Methyl methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Ethyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propyl acetate, methyl butoxyacetate, butyl Ethyl oxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, Methyl 2-butoxypropionate, 2- Ethyl oxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-B Butyl oxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butyl Methyl oxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate. This compound may be used singly or in combination of two or more kinds thereof.
用於使上述單體聚合成丙烯酸共聚物的聚合引發劑係自由基聚合引發劑,且其具體例子包括2,2-偶氮雙異丁腈、2,2-偶氮(2,4-二甲基戊腈)、2,2-偶氮(4-甲氧基-2,4- 二甲基戊腈)、1,1-偶氮(環己烷-1-腈)、及二甲基2,2-偶氮異丁酸酯。A polymerization initiator for polymerizing the above monomer into an acrylic copolymer is a radical polymerization initiator, and specific examples thereof include 2,2-azobisisobutyronitrile and 2,2-azo (2,4-di) Methylvaleronitrile), 2,2-azo (4-methoxy-2,4- Dimethylvaleronitrile), 1,1-azo (cyclohexane-1-carbonitrile), and dimethyl 2,2-azoisobutyrate.
於本發明中,(c)光引發劑的例子包括Irgacure 369、Irgacure 651、Irgacure 907、Darocur TPO、Irgacure 819、三井、苯偶姻、苯乙酮、咪唑、及呫噸酮。In the present invention, examples of the (c) photoinitiator include Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, Mitsui, benzoin, acetophenone, imidazole, and xanthone.
光引發劑的具體例子包括2,4-雙三氯甲基-6-對甲氧基苯乙烯基-s-三井、2-對甲氧基苯乙烯基-4,6-雙三氯甲基-s-三井、2,4-三氯甲基-6-三井、2,4-三氯甲基-4-甲基萘基-6-三井、二苯甲酮、對(二乙基胺基)二苯甲酮、2,2-二氯-4-苯氧基苯乙酮、2,2-二乙氧基苯乙酮、2-十二基噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、及2,2-雙-2-氯苯基-4,5,4,5-四苯基-2-1,2-雙咪唑。此化合物可單獨使用或以其二或多種的組合使用。Specific examples of the photoinitiator include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-tripper, 2-p-methoxystyryl-4,6-bistrichloromethyl -s-Mituto, 2,4-trichloromethyl-6-tripby, 2,4-trichloromethyl-4-methylnaphthyl-6-tripper, benzophenone, p-diethylamino Benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethyl Thioxanthone, 2,4-diethylthioxanthone, and 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole. This compound may be used singly or in combination of two or more kinds thereof.
以100重量份的丙烯酸共聚物為基準,光引發劑的用量為0.001~30重量份,且較佳為0.01~20重量份。若其量少於0.001重量份,則歸因於低敏感性而減少厚度。相反地,若量超過30重量份,則儲存穩定性變成有問題,而且會增加硬化度,在顯影後不宜地減少圖案的黏著性。The photoinitiator is used in an amount of 0.001 to 30 parts by weight, based on 100 parts by weight of the acrylic copolymer, and preferably 0.01 to 20 parts by weight. If the amount is less than 0.001 parts by weight, the thickness is reduced due to low sensitivity. On the other hand, if the amount exceeds 30 parts by weight, the storage stability becomes problematic, and the degree of hardening is increased, and the adhesion of the pattern is undesirably reduced after development.
於本發明中,(d)具有乙烯性不飽和鍵的多官能單體係具有至少二個乙烯性雙鍵的可交聯單體,且其例子包括1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、乙二醇二丙烯酸酯、三羥甲基丙烷二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、二季戊四醇 六丙烯酸酯、二季戊四醇三丙烯酸酯、二季戊四醇二丙烯酸酯、山梨糖醇三丙烯酸酯、雙酚A二丙烯酸酯衍生物、二季戊四醇聚丙烯酸酯、及其甲基丙烯酸酯。In the present invention, (d) a polyfunctional single system having an ethylenically unsaturated bond, a crosslinkable monomer having at least two ethylenic double bonds, and examples thereof include 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol Diacrylate, polyethylene glycol diacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol triacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, and methacrylate thereof.
以100重量份的丙烯酸共聚物為基準,具有乙烯性不飽和鍵的多官能單體之用於為10~100重量份,且較佳為10~60重量份。若其量少於10重量份,則感光性樹脂的硬化度低,使得其難以實現接觸孔及圖案。相反地,若量超過100重量份,則硬化度不必要地增加,在顯影後不宜地減少圖案及接觸孔的解析度。The polyfunctional monomer having an ethylenically unsaturated bond is used in an amount of 10 to 100 parts by weight, and preferably 10 to 60 parts by weight based on 100 parts by weight of the acrylic copolymer. If the amount is less than 10 parts by weight, the degree of hardening of the photosensitive resin is low, making it difficult to achieve contact holes and patterns. On the contrary, if the amount exceeds 100 parts by weight, the degree of hardening is unnecessarily increased, and the resolution of the pattern and the contact hole is undesirably reduced after development.
於本發明中,(e)含有環氧基或胺基的矽系化合物之例子包括(3-縮水甘油氧基丙基)三甲氧基矽烷、(3-縮水甘油氧基丙基)三乙氧基矽烷、(3-縮水甘油氧基丙基)甲基二甲氧基矽烷、(3-縮水甘油氧基丙基)二甲基乙氧基矽烷、3,4-環氧丁基三甲氧基矽烷、3,4-環氧丁基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、及胺基丙基三甲氧基矽烷,其可單獨使用或以其二或多種的組合使用。In the present invention, (e) examples of the oxime compound containing an epoxy group or an amine group include (3-glycidoxypropyl)trimethoxynonane, (3-glycidoxypropyl)triethoxylate. Baseline, (3-glycidoxypropyl)methyldimethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane, 3,4-epoxybutyltrimethoxy Decane, 3,4-epoxybutyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltri Ethoxy decane, and aminopropyl trimethoxy decane, which may be used singly or in combination of two or more kinds thereof.
以100重量份的丙烯酸共聚物為基準,含有環氧基或胺基的矽系化合物之用量為0.0001~5重量份,且較佳為0.005~2重量份。若其量少於0.0001重量份,則在硬化程序後,ITO電極與感光性樹脂之間的黏著性變少,且耐熱性減低。相反地,若量超過5重量份,則在顯影程序後導致在顯影劑中未曝光部分的白化及圖案和接觸孔的浮渣。The oxime compound containing an epoxy group or an amine group is used in an amount of 0.0001 to 5 parts by weight, and preferably 0.005 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer. When the amount is less than 0.0001 part by weight, the adhesion between the ITO electrode and the photosensitive resin is reduced after the curing process, and the heat resistance is lowered. On the contrary, if the amount exceeds 5 parts by weight, whitening of the unexposed portion in the developer and scum of the pattern and the contact hole are caused after the development process.
於本發明中,(f)溶劑係用於平坦化絕緣膜及防止塗層 污斑的產生,因此形成均勻的圖案輪廓。In the present invention, (f) a solvent is used for planarizing an insulating film and preventing coating The generation of stains thus forms a uniform pattern outline.
溶劑的例子包括:醇類,如甲醇、乙醇等;醚類,如四氫呋喃等;二醇醚類,如乙二醇單甲基醚、乙二醇單乙基醚等;乙基二醇烷基醚醋酸酯類,如甲基溶纖劑醋酸酯、乙基溶纖劑醋酸酯等;二乙二醇類,如二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇二甲基醚等;丙二醇單烷基醚類,如丙二醇甲基醚、丙二醇乙基醚、丙二醇丙基醚、丙二醇丁基醚等;丙二醇烷基醚醋酸酯類,如丙二醇甲基醚醋酸酯、丙二醇乙基醚醋酸酯、丙二醇丙基醚醋酸酯、丙二醇丁基醚醋酸酯等;丙二醇烷基醚丙酸酯類,如丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等;芳香族烴類,如甲苯、二甲苯等;酮類,如甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮等;及酯類,如醋酸甲酯、醋酸乙酯、醋酸丙酯、醋酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸酯乙、羥基醋酸甲酯、羥基醋酸乙酯、羥基醋酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸丙酯、乙氧基醋酸丁酯、丙氧基醋酸甲酯、丙氧基醋酸乙酯、丙氧基醋酸丙酯、丙氧基醋酸丁酯、丁氧基醋酸甲酯、氧基醋酸乙酯、丁氧基醋酸丙酯、丁氧基醋酸丁酯、2-甲氧基丙 酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸酯甲、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等。Examples of the solvent include: alcohols such as methanol, ethanol, etc.; ethers such as tetrahydrofuran, etc.; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.; ethyl glycol alkyl group Ether acetates, such as methyl cellosolve acetate, ethyl cellosolve acetate, etc.; diethylene glycols, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol dimethyl ether or the like; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc.; propylene glycol alkyl ether acetates such as propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol alkyl ether propionate such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate , propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4- Methyl-2-pentanone, etc.; and esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2- Ethyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate Ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3 Methyl methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Ethyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propyl acetate, methyl butoxyacetate, oxygen Ethyl acetate, butyl oxyacetate, butyl butoxyacetate, 2-methoxy propyl Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropane Butyl acrylate, butyl 2-butoxypropionate, 3-methoxypropionate methyl, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-ethoxypropane Methyl ester, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropane Ethyl acetate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropane Acid propyl ester, butyl 3-butoxypropionate, and the like.
作為溶劑,特別適用的是至少一種選自於二醇醚、伸乙基烷醚醋酸酯及二乙二醇,其就與各成分的溶解性、反應性及塗膜的形成容易性而言係有利的。As the solvent, at least one selected from the group consisting of glycol ethers, ethyl ethoxide ether and diethylene glycol is used, and it is compatible with the solubility of each component, reactivity, and ease of formation of a coating film. advantageous.
溶劑的用量係使得感光性樹脂組成物的固體含量範圍成為10~50重量份。滿足上述固體含量範圍要求的組成物較佳係在使用0.1~0.2μm微孔過濾器過濾後而使用。較宜地,溶劑的用量係使得組成物的固體含量範圍成為15~40重量份。若組成物的固體含量少於10重量份,則塗層厚度變低,且塗層的平坦性變低。相反地,若固體含量超過50重量份,則塗層厚度將減少,且塗覆裝置在塗佈過程中可能受到負荷。The amount of the solvent is such that the solid content of the photosensitive resin composition is in the range of 10 to 50 parts by weight. The composition satisfying the above requirements of the solid content range is preferably used after being filtered using a 0.1 to 0.2 μm micropore filter. Preferably, the amount of the solvent is such that the solid content of the composition ranges from 15 to 40 parts by weight. If the solid content of the composition is less than 10 parts by weight, the coating thickness becomes low, and the flatness of the coating becomes low. Conversely, if the solid content exceeds 50 parts by weight, the coating thickness will be reduced, and the coating device may be subjected to a load during the coating process.
而且,本發明的感光性樹脂組成物,若須要則可包含與其可相容的添加劑,如熱聚合抑制劑或消泡劑,且可額外地包含顏料,視其最後用途而定。例如,黑色矩陣用的 光阻或彩色濾光片用的光阻,其為用於形成TFT-LCD的影像之材料,係藉由組合本發明的組成物與顏料來形成。而且,如顏料的類型可適當地變化,視黑色矩陣或彩色濾光片用的光阻之最後用而定,且可應用有機顏料及有機顏料。Further, the photosensitive resin composition of the present invention may contain an additive compatible therewith, such as a thermal polymerization inhibitor or an antifoaming agent, if necessary, and may additionally contain a pigment depending on its final use. For example, for black matrices A photoresist for a photoresist or a color filter which is a material for forming an image of a TFT-LCD is formed by combining the composition of the present invention and a pigment. Moreover, the type of the pigment may be appropriately changed depending on the final use of the photoresist for the black matrix or the color filter, and an organic pigment and an organic pigment may be applied.
此外,本發明提供一種TFT-LCD,其含有如上述的有機-無機混成感光性樹脂組成物之硬化體。Further, the present invention provides a TFT-LCD comprising a hardened body of the organic-inorganic hybrid photosensitive resin composition as described above.
形成TFT-LCD的圖案之方法包括由鈍化膜用的有機-無機混成感光性樹脂組成物、罩面層用的光阻、黑色矩陣用的光阻、柱狀間隔物用的光阻,彩色濾光片用的光阻來形成有機絕緣膜,因此製造TFT-LCD,而且方法之特徵為使用有機-無機混成感光性樹脂組成物。A method of forming a pattern of a TFT-LCD includes an organic-inorganic hybrid photosensitive resin composition for a passivation film, a photoresist for an overcoat layer, a photoresist for a black matrix, a photoresist for a column spacer, and a color filter. The photoresist for the light sheet is used to form an organic insulating film, and thus a TFT-LCD is manufactured, and the method is characterized in that an organic-inorganic hybrid photosensitive resin composition is used.
具體地,以下說明使用有機-無機混成感光性樹脂組成物來形成TFT-LCD的圖案之方法。Specifically, a method of forming a pattern of a TFT-LCD using an organic-inorganic hybrid photosensitive resin composition will be described below.
首先,藉由噴霧、輥對輥塗覆或回轉塗覆,將本發明的感光性樹脂組成物塗佈到基板的表面上,然後經由預烘烤以去除溶劑,而形成塗膜。而且該預烘烤係在70~110℃進行1~15分鐘。First, the photosensitive resin composition of the present invention is applied onto the surface of a substrate by spraying, roll-to-roll coating or spin coating, and then a solvent is removed by prebaking to form a coating film. Moreover, the prebaking is carried out at 70 to 110 ° C for 1 to 15 minutes.
然後,經過已經作成的圖案,用可見光、VU光、遠紅外光、電子束或X射線來照射所形成的塗膜,接著用顯影劑來顯影以去除不要的部分,而獲得指定的圖案。Then, the formed coating film is irradiated with visible light, VU light, far infrared light, electron beam or X-ray through a pattern which has been created, and then developed with a developer to remove unnecessary portions to obtain a prescribed pattern.
顯影劑包含鹼性水溶液,且其例子包括:無機鹼,如氫氧化鈉、氫氧化鉀,碳酸鈉等;一級胺,如正丙胺等;二級胺,如二乙胺、正丙胺等;三級胺,如三甲胺、甲基二乙基胺、二甲基乙基胺、三乙胺等;醇胺,如二甲基乙 醇胺、甲基二乙醇胺、三乙醇胺等;及四級銨鹽,如氫氧化四甲基銨、氫氧化四乙銨等。藉由將鹼性化合物以0.1~10重量份的濃度來溶解而使用顯影劑,且可添加指定量的水性有機溶劑,如甲醇或乙醇,及界面活性劑。The developer contains an alkaline aqueous solution, and examples thereof include: an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc.; a primary amine such as n-propylamine; a secondary amine such as diethylamine, n-propylamine, etc.; Alkamines such as trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc.; alkanolamines such as dimethylamine Alcoholamine, methyldiethanolamine, triethanolamine, etc.; and quaternary ammonium salts, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. The developer is used by dissolving the basic compound in a concentration of 0.1 to 10 parts by weight, and a specified amount of an aqueous organic solvent such as methanol or ethanol, and a surfactant may be added.
於使用上述顯影劑的顯影過程後,使用超純水來進行30~90秒的清洗,因此去除不要的部分,然後進行乾燥,因此形成圖案。用於UV光照射該圖案,然後使用加熱器如烘箱在150~250℃加熱30~90分鐘,藉以獲得最終圖案。After the development process using the above developer, ultrapure water is used for the cleaning for 30 to 90 seconds, so that the unnecessary portion is removed and then dried, thereby forming a pattern. The pattern is irradiated with UV light and then heated at 150 to 250 ° C for 30 to 90 minutes using a heater such as an oven to obtain a final pattern.
依照本發明的有機-無機混成絕緣膜係表現低介電常數及優異的抗濕性、黏著性、耐熱性、絕緣性、平坦性及耐化學性,因此適用作為形成LCD之影像用的材料,而且在形成LCD的有機-無機混成鈍化絕緣膜後,顯示低介電常數及優異的抗濕性、黏著性及耐熱性,因此適合當作鈍化絕緣膜。再者,該有機-無機混成絕緣膜係可用作為罩面層用的光阻樹脂、黑色矩陣用的光阻樹脂、柱狀間隔物用的光阻樹脂、彩色濾光片用的光阻樹脂,因此實現高的耐熱性、黏著性等。The organic-inorganic hybrid insulating film according to the present invention exhibits a low dielectric constant and excellent moisture resistance, adhesion, heat resistance, insulation, flatness, and chemical resistance, and thus is suitable as a material for forming an image for an LCD. Further, after forming an organic-inorganic hybrid passivation insulating film of an LCD, it exhibits a low dielectric constant and excellent moisture resistance, adhesion, and heat resistance, and thus is suitable as a passivation insulating film. Further, the organic-inorganic hybrid insulating film can be used as a photoresist resin for an overcoat layer, a photoresist resin for a black matrix, a photoresist resin for a column spacer, and a photoresist resin for a color filter. Therefore, high heat resistance, adhesion, and the like are achieved.
經由以下的實施例可更佳地瞭解本發明,該些實施例用於說明而非構成本發明的限制。The invention is better understood by the following examples, which are intended to illustrate and not to limit the invention.
於具有pH已經調到3~5的酸性範圍之膠態無機材料中,添加1~120重量份的甲基三甲氧基矽烷(MTMS)或乙烯基三甲氧基矽烷(VTMS),其係經乙醇所稀釋的有機矽烷,以便有機矽烷與無機奈米粒子的表面反應,去除水,然後 添加有機溶劑,因此使得反應介質成為疏水性。In a colloidal inorganic material having an acidic range whose pH has been adjusted to 3 to 5, 1 to 120 parts by weight of methyltrimethoxydecane (MTMS) or vinyltrimethoxydecane (VTMS), which is ethanol The diluted organic decane is such that the organic decane reacts with the surface of the inorganic nanoparticle to remove water, and then The organic solvent is added, thus making the reaction medium hydrophobic.
而且,MTMS扮演控制無機材料的表面之疏水性程度的角色,方式為當MTMS的甲氧基與膠態無機粒子的表面反應時,甲基係暴露於其表面,因此將膠態無機材料轉化成可分散在有機樹脂中的形式。此外,VTMS的功能為當VTMS的三個甲氧基與疏水性膠態無機材料的界面之OH基進行縮合反應時,乙烯基變成暴露出,因此疏水性膠態無機粒子可形成具有乙烯基或其它反應基的膠態無機溶膠。Moreover, MTMS plays a role in controlling the degree of hydrophobicity of the surface of the inorganic material in such a manner that when the methoxy group of the MTMS reacts with the surface of the colloidal inorganic particles, the methyl group is exposed to the surface thereof, thereby converting the colloidal inorganic material into A form that can be dispersed in an organic resin. In addition, the function of VTMS is that when the three methoxy groups of VTMS are condensed with the OH group at the interface of the hydrophobic colloidal inorganic material, the vinyl group becomes exposed, and thus the hydrophobic colloidal inorganic particles can be formed to have a vinyl group or Colloidal inorganic sols of other reactive groups.
在裝設有冷卻管及攪拌器的燒瓶內,加入10重量份的2,2’-偶氮(2,4-二甲基戊腈)、200重量份的丙二醇單甲基醚醋酸酯、20重量份的甲基丙烯酸、35重量份的甲基丙烯酸縮水甘油酯、15重量份的甲基丙烯酸甲酯、及30重量份的苯乙烯,用氮氣沖洗,然後徐徐攪拌。將反應溶液加熱到62℃,然後將此溫度維持5小時,因此製備一種含有丙烯酸共聚物的聚合物溶液。10 parts by weight of 2,2'-azo (2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 20 in a flask equipped with a cooling tube and a stirrer Parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 15 parts by weight of methyl methacrylate, and 30 parts by weight of styrene were washed with nitrogen and then slowly stirred. The reaction solution was heated to 62 ° C and then maintained at this temperature for 5 hours, thus preparing a polymer solution containing an acrylic copolymer.
將所製備的丙烯酸共聚物以液滴加到5,000重量份的己烷中,進行沈澱、過濾、分離,添加200重量份的丙酸酯,然後加熱到30℃,因此獲得具有45重量份的固體含量及11,000的重量平均分子量之最終聚合物。重量平均分子量係使用GPC以聚苯乙烯換算。The prepared acrylic copolymer was added dropwise to 5,000 parts by weight of hexane, precipitated, filtered, separated, and 200 parts by weight of propionate was added, followed by heating to 30 ° C, thereby obtaining 45 parts by weight of solid. The final polymer of the content and a weight average molecular weight of 11,000. The weight average molecular weight is converted to polystyrene using GPC.
混合100重量份的含有丙烯酸共聚物的聚合物溶液、15重量份當作光引發劑的Irgacure 819、40重量份當作多 官能單體的二季戊四醇六丙烯酸酯及10重量份的三羥甲基丙烷三丙烯酸酯、1重量份的當作矽系化合物的2-(3,4-環氧環己基)乙基三甲氧基矽烷、及2重量份當作矽系界面活性劑的F171。然後,於此混合物內,加入二乙二醇二甲基醚,量為使得固體含量成為35重量份,藉以溶解混合物。Mix 100 parts by weight of a polymer solution containing an acrylic copolymer, 15 parts by weight of Irgacure 819 as a photoinitiator, and 40 parts by weight as a plurality Dipentaerythritol hexaacrylate of a functional monomer and 10 parts by weight of trimethylolpropane triacrylate, 1 part by weight of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy as a lanthanide compound Decane, and 2 parts by weight of F171 as a lanthanide surfactant. Then, in this mixture, diethylene glycol dimethyl ether was added in an amount such that the solid content became 35 parts by weight to thereby dissolve the mixture.
所獲得丙烯酸共聚物與實施例1的無機溶膠以95:5的重量比進行混合。The obtained acrylic copolymer was mixed with the inorganic sol of Example 1 in a weight ratio of 95:5.
使用0.2μ m的微孔過濾器來過濾所獲得的有機-無機混成感光性樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。The obtained organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm micropore filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
如實施例2中製備丙烯酸共聚物,及如實施例1中製備無機溶膠。將丙烯酸共聚物與無機溶膠以80:20的重量比進行混合,因此獲得一種有機-無機混成感光性樹脂組成物。使用0.2μm的微孔過濾器來過濾有機-無機混成感光性樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 80:20, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
如實施例2中製備丙烯酸共聚物,及如實施例1中製備無機溶膠。將丙烯酸共聚物與無機溶膠以60:40的重量比進行混合,因此獲得一種有機-無機混成感光性樹脂組成物。使用0.2μm的微孔過濾器來過濾有機-無機混成感光性 樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 60:40, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. Filtering organic-inorganic hybrid photosensitivity using a 0.2 μm micropore filter The resin composition was used to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
如實施例2中製備丙烯酸共聚物,及如實施例1中製備無機溶膠。將丙烯酸共聚物與無機溶膠以40:60的重量比進行混合,因此獲得一種有機-無機混成感光性樹脂組成物。使用0.2μm的微孔過濾器來過濾有機-無機混成感光性樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 40:60, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
如實施例2中製備丙烯酸共聚物,及如實施例1中製備無機溶膠。將丙烯酸共聚物與無機溶膠以20:80的重量比進行混合,因此獲得一種有機-無機混成感光性樹脂組成物。使用0.2μm的微孔過濾器來過濾有機-無機混成感光性樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 20:80, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. The organic-inorganic hybrid photosensitive resin composition was filtered using a 0.2 μm microporous filter to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
如實施例2中製備丙烯酸共聚物,及如實施例1中製備無機溶膠。將丙烯酸共聚物與無機溶膠以10:90的重量比進行混合,因此獲得一種有機-無機混成感光性樹脂組成物。使用0.2μm的微孔過濾器來過濾有機-無機混成感光性 樹脂組成物,以去除雜質,而且過濾後的感光性樹脂組成物具有15cps的黏度。若使用其來形成薄膜,則將厚度設定在0.5~5.0μm,視塗佈速率而定。An acrylic copolymer was prepared as in Example 2, and an inorganic sol was prepared as in Example 1. The acrylic copolymer and the inorganic sol were mixed at a weight ratio of 10:90, thereby obtaining an organic-inorganic hybrid photosensitive resin composition. Filtering organic-inorganic hybrid photosensitivity using a 0.2 μm micropore filter The resin composition was used to remove impurities, and the filtered photosensitive resin composition had a viscosity of 15 cps. If it is used to form a film, the thickness is set to 0.5 to 5.0 μm depending on the coating rate.
塗佈實施例3至8的各有機-無機混成感光性樹脂組成物之塗料溶液,且經由以下方法來評估其性質。結果顯示於以下表1中。A coating solution of each of the organic-inorganic hybrid photosensitive resin compositions of Examples 3 to 8 was applied, and its properties were evaluated by the following methods. The results are shown in Table 1 below.
在玻璃基板上,用旋塗機來塗佈實施例3至8的各感光性樹脂組成物溶液,然後在加熱板上於90℃預烘烤2分鐘,因此形成薄膜。On each of the photosensitive resin composition solutions of Examples 3 to 8, the solutions of the photosensitive resin compositions of Examples 3 to 8 were applied by a spin coater, and then prebaked on a hot plate at 90 ° C for 2 minutes, thereby forming a film.
用指定的圖案光罩來覆蓋薄膜,然後用在365nm具有15mW/cm2 的強度之UV光來照射6秒。之後,用0.38重量份的氫氧化四甲銨之水溶液,在25℃將薄膜顯影2分鐘,然後用超純水洗1分鐘。The film was covered with a designated pattern mask and then irradiated with UV light having a intensity of 15 mW/cm 2 at 365 nm for 6 seconds. Thereafter, the film was developed with an aqueous solution of 0.38 parts by weight of tetramethylammonium hydroxide at 25 ° C for 2 minutes, and then washed with ultrapure water for 1 minute.
用在365nm具有15mW/cm2 的強度之UV光來照射經顯影的圖案34秒,在120℃進行中間烘烤3分鐘,然後在220℃的烘箱中加熱60分鐘以使硬化,藉以得到一種圖案薄膜。The developed pattern was irradiated with UV light having a intensity of 15 mW/cm 2 at 365 nm for 34 seconds, intermediate baking was performed at 120 ° C for 3 minutes, and then heated in an oven at 220 ° C for 60 minutes to harden, thereby obtaining a pattern. film.
(a)耐熱性-刮擦最終圖案薄膜,及使用TGA來測量5wt%的重量損失溫度。當5wt%的重量損失溫度為300℃或更高時,評估耐熱性為優異,當5wt%的重量損失溫度為280℃或更高時,評估為良好,當5wt%的重量損失溫度為250℃或更高時,評估為尚可,而且當5wt%的重量損失溫度低於250℃時,評估為差。(a) Heat resistance - scratching the final pattern film, and measuring the weight loss temperature of 5 wt% using TGA. When the weight loss temperature of 5 wt% was 300 ° C or higher, the heat resistance was evaluated to be excellent, and when the weight loss temperature of 5 wt% was 280 ° C or higher, it was evaluated as good, and when the weight loss temperature of 5 wt% was 250 ° C Or higher, it was evaluated as acceptable, and when the weight loss temperature of 5 wt% was lower than 250 ° C, the evaluation was poor.
(b)硬度-在玻璃上形成塗膜,及依照ADTM D3363來測量其表面的鉛筆硬度。(b) Hardness - A coating film was formed on the glass, and the pencil hardness of the surface thereof was measured in accordance with ADTM D3363.
(c)透光率-在如(a)的耐熱性之測量中的預烘烤過程後,具有3μm的厚度之塗膜的可見光吸收光譜。在400nm的光之透光率為98%或更高係評估為優異,在94%或更高但低於98%係評估為良好,在92%或更高但低於94%係評估為尚可,而且低於92%係評估為差。(c) Light transmittance - a visible light absorption spectrum of a coating film having a thickness of 3 μm after the prebaking process in the measurement of heat resistance as in (a). The light transmittance of light at 400 nm is 98% or higher, which is evaluated as excellent, at 94% or higher but lower than 98%, it is evaluated as good, and at 92% or higher but lower than 94%, it is evaluated as Yes, and below 92% are evaluated as poor.
(d)黏著性-使Mo/Al/ITO基板之最終硬化的塗膜接受使用3M膠帶的膠黏試驗。將塗膜切成具有指定大小的100單元,之後以3M膠帶來黏貼,然後徐徐地分離。當每100單元中的殘留單元數目為95或更多時,評估為優異,當殘留單元數目為90或更多時,評估為良好,當殘留單元數目為80或更多時,評估為尚可,而且當殘留單元數目少於80時,評估為差。(d) Adhesion - The final cured film of the Mo/Al/ITO substrate was subjected to an adhesion test using a 3M tape. The coating film was cut into 100 units having a specified size, and then adhered with 3M tape, and then slowly separated. When the number of residual units per 100 units is 95 or more, it is evaluated as excellent, when the number of residual units is 90 or more, it is evaluated as good, and when the number of residual units is 80 or more, it is evaluated as acceptable. And when the number of residual units is less than 80, it is evaluated as poor.
(e)平坦性-於玻璃上形成塗膜,而且使用厚度計來測定其約100點的各厚度。厚度差異小於1%則評估平坦性為優異,厚度差異小於2%則評估平坦性為良好,厚度差異小於3%則評估平坦性為尚可,厚度差異為3%或更大則評估平坦性為差。藉此,可確認分散穩定性及使用球磨機所獲得的丙烯酸共聚物與金屬化合物分散體之間的金屬化合物之沈澱。(e) Flatness - A coating film was formed on the glass, and each thickness of about 100 points was measured using a thickness gauge. When the thickness difference is less than 1%, the flatness is evaluated to be excellent, and when the thickness difference is less than 2%, the flatness is evaluated to be good, and when the thickness difference is less than 3%, the flatness is evaluated as acceptable. When the thickness difference is 3% or more, the flatness is evaluated. difference. Thereby, the dispersion stability and the precipitation of the metal compound between the acrylic copolymer and the metal compound dispersion obtained by using a ball mill can be confirmed.
(f)介電常數-測量電容器的電容,及藉由以下方程式來測定。為此目的,以指定的厚度來形成介電膜,及使用阻抗分析器來測量其電容,而且由以下方程式來計算介電常數。(f) Dielectric constant - The capacitance of the capacitor was measured and determined by the following equation. For this purpose, a dielectric film is formed at a specified thickness, and an impedance is measured using an impedance analyzer, and the dielectric constant is calculated by the following equation.
如由表1可明知,其顯示如上述所製備的有機-無機混成感光性樹脂組成物之性質,實施例3至8的樹脂組成物表現高耐熱性及硬度、優異的平坦性及介電常數等級、以及良好的透光率及黏著性。As is apparent from Table 1, it shows the properties of the organic-inorganic hybrid photosensitive resin composition prepared as described above, and the resin compositions of Examples 3 to 8 exhibit high heat resistance and hardness, excellent flatness, and dielectric constant. Grade, and good light transmittance and adhesion.
特別地,經由穩定地混合無機溶膠化合物,可確保感光性樹脂的塗層平坦性及儲存穩定性。使用無機溶膠係產生一種具有低介電常數的有機-無機混成感光性樹脂組成物。In particular, by stably mixing the inorganic sol compound, coating flatness and storage stability of the photosensitive resin can be ensured. The use of an inorganic sol produces an organic-inorganic hybrid photosensitive resin composition having a low dielectric constant.
因此,在使用本發明的有機-無機混成感光性樹脂組成物當作TFT-LCD的鈍化絕緣膜中,可確認出現優異的耐熱性、硬度、平坦性及介電常數等級,以及良好的透光率及黏著性。Therefore, in the passivation insulating film of the TFT-LCD using the organic-inorganic hybrid photosensitive resin composition of the present invention, it is confirmed that excellent heat resistance, hardness, flatness, dielectric constant level, and good light transmission are observed. Rate and adhesion.
如前述,本發明提供有機-無機混成感光性樹脂組成物及含其硬化體的LCD。依照本發明,有機-無機混成感光性樹脂組成物具有低介電常數、優異的耐熱性、絕緣性、平坦性及耐化學性、以及硬度,因此適用作為形成LCD之影像用的材料,而且在形成LCD的鈍化有機絕緣膜後係表現高的硬度、耐熱性、適當的絕緣性及平坦性,因此適合充當有機絕緣膜。再者,利用感光性樹脂組成物於罩面層用的光阻樹脂、黑色矩陣用的光阻樹脂、柱狀間隔物用的光阻樹脂、彩色濾光片用的光阻樹脂中,以便增進耐熱性、硬度等。As described above, the present invention provides an organic-inorganic hybrid photosensitive resin composition and an LCD containing the same. According to the present invention, the organic-inorganic hybrid photosensitive resin composition has a low dielectric constant, excellent heat resistance, insulation, flatness, chemical resistance, and hardness, and thus is suitable as a material for forming an image of an LCD, and The passivation of the organic insulating film of the LCD exhibits high hardness, heat resistance, proper insulation, and flatness, and thus is suitable as an organic insulating film. Further, a photosensitive resin composition is used for the photoresist resin for the overcoat layer, the photoresist resin for the black matrix, the photoresist resin for the column spacer, and the photoresist resin for the color filter, in order to enhance Heat resistance, hardness, etc.
雖然為了說明之目的,已經揭示本發明的較佳具體態樣,惟熟習該項技術者將瞭解在不脫離如所附申請專利範圍所揭示的本發明之範疇與精神內,可能有各種修飾、增加及替代例。Although the preferred embodiment of the present invention has been disclosed for the purpose of illustration, it will be understood by those skilled in the art that various modifications may be made without departing from the scope and spirit of the invention as disclosed in the appended claims. Additions and alternatives.
Claims (10)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020070071201A KR100911889B1 (en) | 2007-07-16 | 2007-07-16 | Photosensitive resin composition with organic~inorganic hybrid and liquid display devices using |
Publications (2)
Publication Number | Publication Date |
---|---|
TW200916969A TW200916969A (en) | 2009-04-16 |
TWI392909B true TWI392909B (en) | 2013-04-11 |
Family
ID=40268699
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW097126860A TWI392909B (en) | 2007-07-16 | 2008-07-16 | Organic-inorganic hybrid photosensitive resin composition and liquid crystal display comprising cured body thereof |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP4961400B2 (en) |
KR (1) | KR100911889B1 (en) |
CN (1) | CN101349867B (en) |
TW (1) | TWI392909B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101475780B1 (en) * | 2008-02-13 | 2014-12-23 | 주식회사 동진쎄미켐 | Organic-inorganic complex resin composition which is useful as a protecting layer |
CN102031026B (en) * | 2009-09-28 | 2012-12-12 | 复旦大学 | Aqueous nano zirconia particle paint and method for preparing paint film thereof |
JP5636839B2 (en) * | 2010-09-16 | 2014-12-10 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulating film, method for forming interlayer insulating film, and display element |
CN103608726B (en) * | 2011-06-08 | 2016-11-09 | 3M创新有限公司 | Comprise the photoresist of the nano-particle of polymer mooring |
CN102294851A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | Hydrophobic scratch-resistant coating on organic polymer surface and preparation method thereof |
CN103034056A (en) * | 2011-10-07 | 2013-04-10 | 住友化学株式会社 | Colored photosensitive resin composition |
CN102643600B (en) * | 2012-04-18 | 2014-09-03 | 上海维凯化学品有限公司 | Ultraviolet light curing coating composition |
TWI477556B (en) * | 2012-06-11 | 2015-03-21 | Chi Mei Corp | Curable resin composition, protective film and liquid crystal display device including the same |
KR101329218B1 (en) * | 2012-10-22 | 2013-11-13 | (주)아이컴포넌트 | A optical transparent composite film for the use of display and manufacturing method thereof |
KR102059489B1 (en) * | 2013-04-10 | 2019-12-26 | 주식회사 동진쎄미켐 | Negative photosensitive organic-inorganic hybrid insulator |
WO2015033880A1 (en) * | 2013-09-04 | 2015-03-12 | 富士フイルム株式会社 | Resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device |
JP6713320B2 (en) | 2016-03-31 | 2020-06-24 | 日揮触媒化成株式会社 | Surface-treated metal oxide sol |
CN114397797A (en) * | 2022-01-11 | 2022-04-26 | 上海玟昕科技有限公司 | Negative photoresist composition containing nano particles |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0627666A (en) * | 1991-12-21 | 1994-02-04 | Hoechst Ag | Radiation-polymerizable mixture and manufacture of solder resist mask |
TW575799B (en) * | 1998-07-14 | 2004-02-11 | Brewer Science Inc | Photosensitive black matrix |
JP2006078826A (en) * | 2004-09-10 | 2006-03-23 | Nippon Kayaku Co Ltd | Photosensitive resin composition |
TW200708894A (en) * | 2005-07-19 | 2007-03-01 | Dongjin Semichem Co Ltd | Photosensitive resin composition comprising organic and inorganic compounds |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100188181B1 (en) * | 1996-12-20 | 1999-06-01 | 서영배 | Photosensitive solder resist composition |
JP4050370B2 (en) * | 1998-01-07 | 2008-02-20 | 株式会社Kri | Inorganic-containing photosensitive resin composition and inorganic pattern forming method |
US20060128853A1 (en) * | 2004-12-13 | 2006-06-15 | General Electric Company | Compositions for articles comprising replicated microstructures |
KR101068111B1 (en) | 2005-01-27 | 2011-09-27 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
-
2007
- 2007-07-16 KR KR1020070071201A patent/KR100911889B1/en not_active IP Right Cessation
-
2008
- 2008-07-15 JP JP2008183905A patent/JP4961400B2/en not_active Expired - Fee Related
- 2008-07-16 CN CN2008101429199A patent/CN101349867B/en not_active Expired - Fee Related
- 2008-07-16 TW TW097126860A patent/TWI392909B/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0627666A (en) * | 1991-12-21 | 1994-02-04 | Hoechst Ag | Radiation-polymerizable mixture and manufacture of solder resist mask |
TW575799B (en) * | 1998-07-14 | 2004-02-11 | Brewer Science Inc | Photosensitive black matrix |
JP2006078826A (en) * | 2004-09-10 | 2006-03-23 | Nippon Kayaku Co Ltd | Photosensitive resin composition |
TW200708894A (en) * | 2005-07-19 | 2007-03-01 | Dongjin Semichem Co Ltd | Photosensitive resin composition comprising organic and inorganic compounds |
Also Published As
Publication number | Publication date |
---|---|
CN101349867A (en) | 2009-01-21 |
JP4961400B2 (en) | 2012-06-27 |
KR100911889B1 (en) | 2009-08-11 |
KR20090007953A (en) | 2009-01-21 |
TW200916969A (en) | 2009-04-16 |
JP2009020520A (en) | 2009-01-29 |
CN101349867B (en) | 2012-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI392909B (en) | Organic-inorganic hybrid photosensitive resin composition and liquid crystal display comprising cured body thereof | |
CN1900821B (en) | Organic-inorganic composite photosensitive resin composition | |
JP4934353B2 (en) | Negative photosensitive resin composition | |
TWI422971B (en) | Negative photosensitive resin composition | |
KR101302508B1 (en) | Negative photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same | |
JP5546775B2 (en) | Organic / inorganic composite resin composition useful as a protective film | |
TWI471697B (en) | Negative photosensitive resin composition | |
CN104937491B (en) | Photosensitive resin composition and method for forming pattern using the same | |
JP2013534326A (en) | Negative photosensitive resin composition | |
TWI677755B (en) | Negative photosensitive resin composition comprising photoreactive silane coupling agent | |
KR101041310B1 (en) | Photosensitive resin composition | |
JP7469024B2 (en) | Positive type photosensitive resin composition | |
TW200427766A (en) | Resin composition, protection film of color filter and its formation method | |
KR101305528B1 (en) | Organic-inorganic composite photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same | |
JP6154398B2 (en) | Photoresist composition | |
CN117215151A (en) | Preparation method and application of negative high refractive index OC photoresist and photo-curing pattern with good hydrophilic performance | |
JP2018095811A (en) | Composite resin composition and composite resin cured product | |
TW201314353A (en) | Composition of white photoresist |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |