CN1781057A - 用于高孔径lcd有机绝缘层的负性抗蚀组合物 - Google Patents
用于高孔径lcd有机绝缘层的负性抗蚀组合物 Download PDFInfo
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- CN1781057A CN1781057A CNA2004800116939A CN200480011693A CN1781057A CN 1781057 A CN1781057 A CN 1781057A CN A2004800116939 A CNA2004800116939 A CN A2004800116939A CN 200480011693 A CN200480011693 A CN 200480011693A CN 1781057 A CN1781057 A CN 1781057A
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- Prior art keywords
- methyl
- ether
- ester
- acid
- organic insulator
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- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 239000012212 insulator Substances 0.000 title claims abstract description 33
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- 229920005989 resin Polymers 0.000 claims abstract description 29
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- 239000000178 monomer Substances 0.000 claims abstract description 11
- -1 α-Jia Jibenyixi Chemical compound 0.000 claims description 49
- 230000007797 corrosion Effects 0.000 claims description 33
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
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- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- XDHOEHJVXXTEDV-UHFFFAOYSA-N 1-ethoxyprop-1-ene Chemical group CCOC=CC XDHOEHJVXXTEDV-UHFFFAOYSA-N 0.000 claims description 2
- LELKUNFWANHDPG-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COCC1CO1 LELKUNFWANHDPG-UHFFFAOYSA-N 0.000 claims description 2
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- GSYWJWFOKRBGQB-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O Chemical compound N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O GSYWJWFOKRBGQB-UHFFFAOYSA-N 0.000 claims description 2
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- 238000005886 esterification reaction Methods 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明揭示了一种用于高孔径LCD有机绝缘层的负性抗蚀组合物。该组合物包括:从具有化学式1和化学式2所示结构的粘结剂用树脂及其混合物中选出的5~40重量份的粘结剂用树脂;包含不饱和脂族基的2~200重量份的多功能单体;和0.005~20重量份的光敏引发剂。在制造高孔径LCD有机绝缘层时,该负性抗蚀组合物呈现出良好的粘着力、紫外线透射率、成膜性、均匀度和图案稳定性。
Description
技术领域
本发明涉及一种高孔径LCD(液晶显示屏,Liquid Crystal Display)有机绝缘层的负性抗蚀组合物,特别是涉及一种用于有机绝缘层的负性抗蚀组合物,该有机绝缘层是在形成高孔径LCD的有机绝缘层时由碱性显影液显影而来,从而形成具有良好金属粘着力、紫外线透射率、成膜性、均匀度和图案稳定性的图案。
背景技术
一般来说,LCD(液晶显示屏)被用作电视或图形显示的显示设备。特别是,有源矩阵式液晶显示屏(active matrix LCD)中,每个象素都提供有开关元件,如TFT(薄膜晶体管,Thin Film Transistor),可具有快速响应特性并允许大数量的象素,因此有助于实现可与CRT(阴极射线管,CathodeRay Tube)媲美的高品质、大尺寸并且色彩丰富的显示屏。
为了使LCD能够获得高品质的显示,对高孔径的改进十分重要。在本发明中,孔径(aperture)被定义为一个象素电极(pixel electrode)面积的实际透光率。
在TFT-LCD领域中,越来越需要大尺寸和高品质,但电池效率的提高满足不了这种需要,因此,正在研究提高液晶透射率的方法。为了提高液晶透射率,采用了许多方法,例如,提高液晶面板孔径、提高偏光板(polarizing plate)的透射率,以及提高颜色过滤器透射率。其中,对于提高液晶面板的方法,在TFT上布置ITO(氧化铟锡,Indium Tin Oxide)象素,使被称为象素电极的、由透明金属制成的电极排布在整个象素区域之上,然后,象素电极的尺寸被放大。采用这一技术时,现有的TFT-LCD的孔径提高了约50~60%,甚至高达80~85%。
为了便于理解,下面结合附图对高孔径TFT-LCD进行详细说明。图1是普通的高孔径TFT-LCD的晶胞(unit cell)的平面示意图。请参阅图1,栅极线2(gate line)横向设置,存储电极线4(storage electrode line)与栅极线2隔开一段距离并与栅极线2平行设置。数据线8(data line)垂直穿过栅极线2和存储电极2。
具有某种图案形状的半导体层6(semiconductor layer)形成于栅极线2之上邻近数据线8的位置,由数据线8引出的漏极9a(drain electrode)与和数据线8一体形成的源极9b(source electrode)相向地设置于半导体层8上并部分重叠。
同时,由ITO制成的象素电极12(pixel electrode)被置于被栅极线2和数据线8分割的象素区内。此时,象素电极12与源极9b接触,并被置于整个象素区之上,与数据线8和栅极线2部分重叠。
图2是沿图1中II-II’线方向的截面图。如图2所示,栅极2a在下层衬底20(lower substrate)上形成,存储电极4a在与栅极2a隔开一段预定距离的位置形成。在下层衬底20的上表面的前端上形成栅极绝缘层5(gate insulator)。采用熟知的工艺在在栅极绝缘层5上半导体层6图案。在半导体层6上形成漏极9a和与数据线8一体形成的源极9b,并且二者互相隔开一段距离。
此外,具有低介电常数的有机绝缘层10被涂覆在下层衬底20的上表面上。有机绝缘层10上提供有接触孔(图中未示),用以将源极暴露。象素电极12在有机绝缘层10上形成,藉由接触孔在与象素区对应的位置与源极9b接触并与栅极2a和数据线8的一部分重叠。这里,有机绝缘层10所起的作用是将象素电极12与数据线8绝缘并且使下层平坦。
在图1中,在形成有机绝缘层时,通常采用正性抗蚀(positive resist)作为绝缘膜。然而,正性抗蚀对金属的粘着力很差并且在显影后成膜性差,从而破坏均匀性。特别是,由于为了提高透光率必须进行紫外线漂白,增加了工艺步骤,从而增加了次品率和粘结时间(tack time),导致产品收得率的降低。
发明内容
本发明旨在于解决现有技术中存在的问题,因此,本发明的目的在于提供一种负性抗蚀组合物,其是在形成高孔径LCD的有机绝缘层时藉由碱性显影液显影而成,从而形成具有良好金属粘着力、紫外线透射率、成膜性、均匀度和图案稳定性的图案。
为了实现上述目的,本发明提供一种用于高孔径LCD有机绝缘层的负性抗蚀组合物,其包括:5-40重量份的粘结剂树脂,该粘结剂树脂是选自具有下列通式1结构的粘结剂树脂、具有下列通式2结构的粘结剂树脂、以及两者的混合物;2-200重量份的具有不饱和脂肪基的多官能单体;以及0.005-20重量份的光敏引发剂。
附图说明
为了使本发明的目的和各个方面更为明晰,更下面结合附图对实施例进行详细说明。
图1是现有技术中具有高孔径的TFT-LCD的晶胞结构的平面示意图。
图2是II-II’线方向的截面图。
具体实施方式
下面对本发明进行更为详细的说明。
用于高孔径LCD有机绝缘层的负性抗蚀组合物,其包括:5-40重量份的粘结剂树脂,该粘结剂树脂是选自具有下列通式1结构的粘结剂树脂、具有下列通式2结构的粘结剂树脂、以及两者的混合物;2-200重量份的具有不饱和脂肪基的多官能单体;以及0.005-20重量份的光敏引发剂。
通式1
在通式1中,x代表氢原子或甲基,Y1代表具有1~16个碳原子的烷基或羟烷基,Y2代表选自于具有下列(I)至(XX)的化学式结构的化合物。
在化学式(I)至(XX)中,R1代表氢原子或甲基,R2代表具有1~10个碳原子的烃,R3代表具有1~10个碳原子的烃,R4代表氢原子或甲基,R53代表具有1~10个碳原子的烃,k代表1~10的正整数。
通式2
在通式2中,重复单元A选自于下列物质:甲基丙烯酸苄基酯(benzylmethacrylate,BZMA)、苯乙烯(styrene,Sty)、α-甲基苯乙烯(α-methylstyrene)、丙烯酸异冰片酯(isobonyl acrylate)和甲基丙烯酸异冰片酯(isobonyl methacrylate,IBMA)、丙烯酸双环戊基酯(dicyclopentanylacrylate)、甲基丙烯酸双环戊基酯dicyclopentanylmethacrylate(DCPMa)、丙烯酸双环戊烯基酯(dicyclopentenyl acrylate)、甲基丙烯酸双环戊烯基酯(dicyclopentenyl methacrylate)、双环戊基乙氧基丙烯酸酯(dicyclopentanylethyloxy acrylate)、双环戊基乙氧基(甲基)丙烯酸酯(dicyclopentanylethyloxy methacrylate)、双环戊烯基乙氧基丙烯酸酯(dicyclopentenylethyloxy acrylate)、双环戊烯基乙氧基(甲基)丙烯酸酯(dicyclopentenylethyloxy methacrylate)等,重复单元B选自于下列物质:甲基丙烯酸缩水甘油酯(glycidyl methacrylate,GMA)、甲基丙烯酸羟乙酯(hydroxylethyl methacrylate,HEMA)、N,N-二甲基-(甲基)丙烯酰胺(dimethylamino methacrylate)、丙烯酰胺(acrylamide、ACAMi)等等;重复单元C为丙烯酸(acrylic acid,AA)或甲基丙烯酸(methacrylic acid,MAA),其中,具有通式2结构的粘结剂树脂含有与A、B和C的排列次序无关的任意共聚物。
具有通式1所示结构粘结剂是一种由包含羧酸的单体和包含双键的单体构成的共聚物。当本发明的包括所述共聚物的抗蚀组合物被施用于衬底上并于其后形成图案时,均匀性非常好,显影后没有如残留物等任何缺陷。换言之,通式1中的Y1是具有1~16个碳原子的烷基或羟烷基,从而提高了粘着力。还有,Y2包含不同于普通丙烯酸共聚物粘结剂树脂的大体积环脂肪族结构,其包含芳香基,从而提高了成膜性,并且由于高玻璃态转化温度提高了耐热性。
较好的是,具有通式1结构的粘结剂树脂具有2,000~50,000的平均分子量,1.0~5.0的多分散性,以及10~400KOH mg/g的酸值。更好的是,其具有5,000~40,000的平均分子量,1.6~3.0的多分散性,以及20~150KOH mg/g的酸值。
还有,通式2的粘结剂树脂表现出与通式1的粘结剂树脂几乎同样的效果。对于通式2的粘结剂树脂来说,另一种重复单元,例如,烷基丙烯酸酯或具有2~16个烷基团烷基甲基丙烯酸酯,如下面的通式3(D)所示,可在本发明的范围内被采用。更具体来说,该重复单元可以是甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸月桂酯、苯乙烯,等等。
通式3
较好的是,具有通式2结构的粘结剂树脂具有2,000~100,000的平均分子量,1.0~5.0的多分散性,以及15~400KOH mg/g的酸值。更好的是,其具有5,000~40,000的平均分子量,1.6~3.0的多分散性,以及30~150KOH mg/g的酸值。
特别是在使用通式1的粘结剂树脂和通式2的粘结剂树脂混合使用时,可能提高图案的硬度,并且白化现象消失,这是由于提高了粘结剂树脂与其他光致抗蚀组分的相容性。
包含不饱和脂肪基的多官能单体包括至少一个选自下列的物质:使用α,β-不饱和羧酸对多元醇进行酯化作用后得到的化合物,其选自下列物质:二(甲基)丙烯酸乙二醇酯(ethylene glycol di(meth)acrylate)、含2~14环氧乙烷基团的聚二甲基丙烯酸乙二醇酯(polyethylene glycoldi(meth)acrylate having 2 to 14 ethyleneoxide groups)、三羟甲基丙烷二(甲基)丙烯酸酯(trimethylolpropane di(meth)acrylate)、三羟甲基丙烷三(甲基)丙烯酸酯(trimemethylolpropanetri(meth)acrylate)、三甲基丙烯酸季戊四醇酯(pentaerythritoltri(meth)acrylate)、四甲基丙烯酸季戊四醇酯(pentaerythritoltetra(meth)acrylate)、含有2~14个环氧丙烷基团的二甲基丙烯酸丙二醇酯(propylene glycol di(meth)acrylate having 2 to 14 propyleneoxidegroups)、五甲基丙烯酸双季戊四醇酯(dipentaerythritolpenta(meth)acrylate)、六甲基丙烯酸双季戊四醇酯(dipentaerythritolhexa(meth)acrylate)、三甲基丙烯酸双季戊四醇酯(dipentaerythritoltri(meth)acrylate);通过向具有缩水甘油基的化合物中加入(甲基)丙烯酸获得的化合物,其是选自下列物质:三羟甲基丙烷三缩水甘油基醚丙烯酸加合物(trimethylolpropane triglycidyl ether acrylic acidadduct)和双酚A二缩水甘油醚丙烯酸加合物(bisphenol A diglycidylether acrylic acid adduct);多聚羧酸的酯类化合物或多异氰酸酯与包含羟基与不饱和脂肪基的加合物,其是选自下列物质:甲基丙烯酸-β-羟基乙酯的邻苯二甲酸二酯加合物(phthalic acid diester of β-hydroxyethyl(meth)acrylate)和甲基丙烯酸-β-羟基乙酯的甲苯二异氰酸酯加合物(toluene diisocyanate adduct of β-hydroxyethyl(meth)acrylate);以及甲基丙烯酸烷基酯((meth)acrylicacidalkyl ester),其是选自:甲基丙烯酸甲酯(methyl(meth)acrylate)、甲基丙烯酸乙酯(ethyl(meth)acrylate)、甲基丙烯酸丁酯(butyl(meth)acrylate)、甲基丙烯酸2-乙基己酯(2-ethylhexyl(meth)acrylate)。其含量为2~200重量份,较好的是5~50重量份。
通过调节包含上述不饱和脂肪基的多官能单体与粘结剂树脂之间的配比,就可以形成用于高孔径LCD的具有高耐热性、高透明度、良好均匀性和图案稳定性的有机绝缘层的负性抗蚀。
还有,通常使用苯乙酮或苯甲酮类型的光敏引发剂。由于彩色光敏引发剂会降低透明度,所以通过使用本身无色但在曝光波长下具有适当感光度的光敏引发剂获得高透明度。通常,根据所使用的紫外线波长,来选择丙烯酸多官能单体的交联反应中所使用的光敏引发剂。由于最常用的水银灯的波长为310~420nm,最好使用生成的根在此波长范围内的光敏引发剂。
对于这种光敏引发剂,较好的是使用苯乙酮、苯甲酮或三嗪类光敏引发剂,如Irgacure 369、Irgacure 651、Irgacure 907、TPO、CGI124、以及EPD/BMS混合物。例如:苯甲酮(benzophenone)、苯基联苯基酮(phenylbiphenyl ketone)、1-羟基-1-苯甲酰基环己烷(1-hydroxy-1-benzoylcyclohexane)、苯偶酰二甲基缩酮(Benzyldimethylketal)、1-苄基-1-二甲基氨基-1-(4-吗啉代-苯甲酰基)丙烷(1-benzyl-1-dimethylamino-1-(4-morpholino-benzoyl)propane)、2-吗啡酚-2-(4-甲基巯基)苯甲酰丙烷(2-morpholyl-2-(4-methylmercapto)benzoylpropane)、噻吨同(Thioxanthone)、1-氯-4-丙氧基噻吨酮(1-chloro-4-propoxythioxanthone)、异丙基噻吨酮(isopropylthioxanthone)、二乙基噻吨酮(diethylthioxanthone)、乙基蒽醌(ethylanthraquinone)、4-苯甲酰基-4-甲基二苯基硫(4-benzoyl-4-methyldiphenylsulfide)、苯偶姻丁醚(Benzoinbutylether)、2-羟基-2-苯甲酰基丙烷(2-hydroxy-2-benzoylpropane)、2-羟基-2-(4-异丙基)苯甲酰基丙烷(2-hydroxy-2-(4-isopropyl)benzoylpropane)、4-丁基苯甲酰基三氯甲烷(4-butylbenzoyltrichloromethane)、4-苯氧基苯甲酰基二氯甲烷(4-phenoxybenzoyldichloromethane)、苯甲酰甲酸甲酯(Methylbenzoyl formate)、1,7-双(9-吖啶)庚烷(1,7-bis(9-acridinyl)heptane)、9-n-丁基-3,6双(2-吗啉代-异丁酰基)咔唑(9-n-butyl-3,6bis(2-morpholino-isobutyroyl)carbazole)、2-甲基-4,6-双(三氯甲基)-s-三嗪(2-methyl-4,6-bis(trichloromethyl)-s-triazine)、2-苯基-4,6-双(三氯甲基)-s-三嗪(2-phenyl-4,6-bis(trichloromethyl)-s-triazine)、2-萘基-4,6-双(三氯甲基)-s-三嗪(2-naphthyl-4,6bis(trichloromethyl)-s-triazine)等。为了改善透明度和照射剂量,光敏引发剂的含量为0.005~20重量份,较好的是0.5~10重量份。
较好的是,在本发明的负性抗蚀组合物中还加入包含环氧或胺基的硅化合物。该硅化合物提高了ITO电极与该组合物之间粘结度,并提高了硬化后的耐热性。该硅化合物包括至少一个选自下列的物质:(3-缩水甘油醚基丙基)三甲氧基硅烷((3-glycidoxypropyl)trimethoxysilane)、(3-缩水甘油醚基丙基)三乙氧基硅烷((3-glycidoxypropyl)triethoxysilane)、(3-缩水甘油醚基丙基)甲基二甲氧基硅烷((3-glycidoxypropyl)methyldimethoxysilane)、(3-缩水甘油醚基丙基)甲基二氧基硅烷((3-glycidoxypropyl)methyldiethoxysilane)、(3-缩水甘油醚基丙基)二甲基甲氧基硅烷((3-glycidoxypropyl)dimethylmethoxysilane)、(3-缩水甘油醚基丙基)二甲基乙氧基硅烷((3-glycidoxypropyl)dimethylethoxysilane)、3,4-环氧丁基三甲氧基硅烷(3,4-epoxybutyltrimethoxysilane)、3,4-环氧丁基三乙氧基硅烷(3,4-epoxybutyltriethoxysilane)、2-(3,4-环氧环己基)乙基三甲氧基硅烷(2-(3,4-epoxycyclohexyl)ethyktrimethoxysilane)、2-(3,4-环氧环己基)乙基三乙氧基硅烷(2-(3,4-epoxycyclohexyl)ethyltriethoxysilane)、氨基丙基三甲氧基硅烷(aminopropyltrimethoxysilane)、等。硅化合物的含量是0.0001~3重量份,较好的是0.005~0.1重量份。
此外,如有必要,本发明的负性抗蚀组合物中可使用添加剂如:光敏剂、热聚合抑制剂、消泡剂和均化剂。
本发明的用于有机绝缘层的负性抗蚀组合物通过依次添加一种溶剂、在衬底上进行旋涂、使用掩膜进行紫外线照射、并使用碱性显影液进行显液,从而形成高孔径LCD的有机绝缘层。较佳的是,添加一种溶剂使本发明的负性抗蚀组合物具有2~30cps的粘度。更佳的是,将粘度调节为10~25cps,这对于控制薄层使之不含针孔更为有利。该溶液至少包括一个选自下列的物质:乙酸乙酯(ethyl acetate)、乙酸丁酯(butyl acetate)、二乙二醇二甲醚(diethylene glycol dimethyl ether)、二乙二醇二甲基乙基醚(diethylene glycol dimethylethyl ether)、甲氧基丙酸甲酯(methylmetboxy propionate)、乙氧基丙酸乙酯(ethylethoxypropionate(EEP))、乳酸乙酯(ethyl lactate)、丙二醇甲醚乙酸酯(propylene glycol methyl ether acetate(PGMEA))、丙二醇甲醚(propylene glycol methyl ether)、丙二醇丙醚(propylene glycol propylether)、甲基溶纤剂乙酸酯(methylcellosolvacetate)、乙基溶纤剂乙酸酯(ethylcellosolvacetate)、二乙二醇甲醚醋酸酯(diethylene glycolmethylacetate)、二乙二醇乙醚醋酸酯(diethylene glycol ethylacetate)、丙酮(acetone)、甲基异丁基酮(methyl isobutyl ketone)、环己酮(cyclohexanone)、二甲基甲酰胺(dimethylformamide(DMF))、N,N-二甲基乙酰胺(N,N-dimethylacetamide(DMAc))、N-甲基吡咯烷酮N-methyl-2-pyrrolidone(NMP))、γ-丁内酯(γ-butyrolactone)、乙醚(diethyl ether)、乙二醇二甲醚(ethylene glycol dimethyl ether)、二甘醇二甲醚(diglyme)、四氢呋喃(tetrahydrofuran(THF))、甲醇(methanol)、乙醇(ethanol)、丙醇(propanel)、异丙醇(isopropanol)、甲基溶纤剂(methylcellosolve)、乙基溶纤剂(ethylcellosolve)、二乙二醇甲醚(diethylene glycol methyl ether)、二乙二醇乙醚(diethyleneglycol ethyl ether)、二丙二醇甲醚(dipropylene glycol methyl ether)、甲苯(toluene)、二甲苯(xyleme)、己烷(hexane)、庚烷(heptane)、辛烷(octane)、。
下面将对本发明进行更为具体的说明。但是,应该理解,不论详细描述还是特定实例,尽管是针对本发明的优选实施例进行的,但也仅起到说明作用,对于本领域技术人员来说,依据本详细说明,在不脱离本发明的精神和范围之内,当可进行各种变化和修饰。
实施例1
根据表1中的组份和含量,将粘结剂和二(聚)季戊四醇六/五丙烯酸酯作为多官能单体加入具有紫外线过滤镜和搅拌器反应器。接着,加入作为光敏引发剂的Irgacure 369、(3-环氧丙基氧丙基)三甲氧基(乙氧基)硅烷、和以树脂全部固体含量为基础的0.1~3重量百分比的添加剂,如熟知的光敏剂、热聚合抑制剂、消泡剂、均化剂,从而制备出用于有机绝缘层的负性抗蚀组合物。然后,在室温下搅拌该负性抗蚀组合物。然后,在该组合物中加入一种溶剂,使粘度为15cps。
在实施例1中,该粘结剂树脂用化学式(1-I)~(1-VI)表示,其中,X和Y1都是甲基,Y2是化学式(I)~(VI)所示的基团(其中R1和R2都是甲基)。
实施例2~25
负性抗蚀组合物采用与实施例1相同的方法制备,只是组合物的种类和含量根据表1和表2有所变化。
比较例1~4
负性抗蚀组合物采用与实施例1相同的方法制备,只是采用通式4的粘结剂树脂取代了通式1,组合物的种类和含量根据表3都有所变化。
通式4
其中p为0.3、q为0.2、r为0.5
表1
在表1中,通式1的粘合剂树脂具有15,000的平均分子量、2.5的多分散性、以及100的酸值;而通式2的粘合剂树脂具有20,000的平均分子量、2.5的多分散性、以及110的酸值
表2
在表2中,通式1的粘合剂树脂具有15,000的平均分子量、2.5的多分散性、以及110的酸值;而通式2的粘合剂树脂具有10,000的平均分子量、2.5的多分散性、以及100的酸值。
表3
在表3中,通式4的粘合剂树脂具有20,000的平均分子量、2.5的多分散性、以及100的酸值。
在一衬底上,如硅圆片或玻璃衬底上,对根据实施例和比较例的负性抗蚀组合物进行评估。对组合物的热性质、透光度(T%,400nm)、均匀性、成膜性、以及图案形成进行如下试验。结果如表4和表5。
(1)热性质
使用旋转涂膜机(spin coater)在衬底上施加负性抗蚀组合物,以800rpm持续8秒,100℃预焙1分钟,以365nm曝光15秒,并在220℃后烘焙30分钟,形成抗蚀层。然后,将形成的抗蚀层放入高压锅,在100℃下熟化1小时。使用网状刀具(Cross Hatch Cutter)对高压锅中熟化的试件进行刻划以便将衬底暴露,用粘结带粘结,然后揭去粘结带。如果衬底上每100个晶胞(cell)中有80个未被揭除,则标记为“合格”,否则标记为“不合格”。
(2)紫外线透光度
使用旋转涂膜机在衬底上施加负性抗蚀组合物,以800rpm持续8秒,100℃预焙1分钟,2.38%TMAH溶液显影60秒,去离子水漂洗,压缩空气吹扫,并在220℃下后烘焙30分钟。这样就形成大约3.5~4.0μm的抗蚀层。在400nm波长下,测量该抗蚀层的紫外线透光度。
(3)成膜性
在衬底上旋涂负性抗蚀组合物。分别测量预焙和后烘焙形成的层之间的厚度比(%)。
(4)图案形成
沿穿孔图案(hole pattern)轴向取形成负性抗蚀图案的硅圆片,并使用电子显微镜观察图案的截面方向。当图案侧壁与衬底的夹角大于55°并且厚度没有减少时,标记为“合格”。当厚度减少时,标记为“TR”(厚度减少)。
(5)耐化学性
使用旋转涂膜机在衬底上施加负性抗蚀组合物,预焙后再后烘焙,形成抗蚀层。在40℃下将形成的抗蚀层浸入剥离器和腐蚀溶液10分钟。然后,检查抗蚀层的透光度和厚度是否有任何变化。如果透光度和厚度没有变化,标注为“合格”,否则标为“不合格”。
表4
实施例 | 粘着力 | 紫外线透光度(400nm)(%) | 成膜性(5) | 图案 | 耐化学性 |
1 | 好 | 98 | 90 | 好 | 好 |
2 | 好 | 98 | 90 | 好 | 好 |
3 | 好 | 96 | 90 | 好 | 好 |
4 | 好 | 96 | 90 | 好 | 好 |
5 | 好 | 97 | 90 | 好 | 好 |
6 | 好 | 97 | 90 | 好 | 好 |
7 | 好 | 96 | 88 | 好 | 好 |
8 | 好 | 96 | 89 | 好 | 好 |
9 | 好 | 97 | 89 | 好 | 好 |
10 | 好 | 97 | 90 | 好 | 好 |
11 | 好 | 97 | 88 | 好 | 好 |
12 | 好 | 97 | 87 | 好 | 好 |
13 | 好 | 97 | 87 | 好 | 好 |
14 | 好 | 97 | 88 | 好 | 好 |
15 | 好 | 97 | 89 | 好 | 好 |
16 | 好 | 97 | 89 | 好 | 好 |
17 | 好 | 98 | 89 | 好 | 好 |
18 | 好 | 96 | 89 | 好 | 好 |
19 | 好 | 98 | 90 | 好 | 好 |
20 | 好 | 97 | 90 | 好 | 好 |
21 | 好 | 97 | 90 | 好 | 好 |
22 | 好 | 96 | 90 | 好 | 好 |
23 | 好 | 96 | 89 | 好 | 好 |
24 | 好 | 96 | 89 | 好 | 好 |
25 | 好 | 96 | 90 | 好 | 好 |
表5
比较例 | 粘着力 | 紫外线透光度(400nm)(%) | 成膜性(5) | 图案 | 耐化学性 |
1 | 坏 | 95 | 80 | TR | 坏 |
2 | 坏 | 96 | 80 | TR | 坏 |
3 | 坏 | 95 | 85 | TR | 坏 |
4 | 坏 | 96 | 80 | TR | 坏 |
如上所述,与普通的抗蚀组合物不同,本发明的负性抗蚀组合物表现出对金属和无机物良好的粘结性、良好的紫外线透光率、成膜性、均匀性和图案稳定性,以及良好的耐热性。
如上述,本发明的负性抗蚀组合物在形成有机绝缘层时,表现出良好的对金属和无机物的附着力、紫外线透光率、成膜性、均匀性和图案稳定性,以及良好的耐热性。而且,由于其透光率高于正性抗蚀的透光率,能够控制好背光的亮度,从而增加电池效率并降低由于色度差异造成的影响。而且,本发明的负性抗蚀组合物能够形成一种有机绝缘层,在本发明的范围内,通过改变粘结剂树脂的结构和组合物配比,使其具有要求的特定物理性质。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许的更动或修饰为等同变化的等效实施例,但是凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (8)
1.一种用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其包括:
5~40重量份的粘结剂树脂,该粘结剂树脂是选自具有下列通式1结构的粘结剂树脂、具有下列通式2结构的粘结剂树脂、以及两者的混合物;
2~200重量份的具有不饱和脂肪基的多官能单体;以及
0.005~20重量份的光敏引发剂;
通式1
其中X是氢原子或甲基,Y1是烷基或羟烷基,其具有1~16个碳原子,并且Y2是选自于具有下列化学式(I)到(XX)结构的化合物;
其中R1是氢原子或甲基,R2是具有1~10个碳原子的烃,R3是具有1~10个碳原子的烃,R4是氢原子或甲基,R5是具有1~10个碳原子的烃,k是0~10的整数;
通式2
其中重复单元A是选自于:甲基丙烯酸苄基酯、苯乙烯、α-甲基苯乙烯、丙烯酸异冰片酯和甲基丙烯酸异冰片酯、丙烯酸双环戊基酯、甲基丙烯酸双环戊基酯、丙烯酸双环戊烯基酯、甲基丙烯酸双环戊烯基酯、双环戊基乙氧基丙烯酸酯、双环戊基乙氧基(甲基)丙烯酸酯、双环戊烯基乙氧基丙烯酸酯、以及双环戊烯基乙氧基(甲基)丙烯酸酯;B是从选自些列物质:甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、N,N-二甲基-(甲基)丙烯酰胺、以及丙烯酰胺;C是丙烯酸或甲基丙烯酸,其中,具有通式2结构的粘结剂树脂含有与A、B和C的排列次序无关的任意共聚物。
2.根据权利要求1所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其中所述的具有通式1结构的粘结剂树脂具有2000~50,000的平均分子量、1.0~5.0的多分散性、以及10~400KOH mg/g的酸值。
3.根据权利要求1所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其中所述的具有通式2结构的粘结剂树脂具有2000~100,000的平均分子量、1.0~5.0的多分散性、以及15~400KOH mg/g的酸值。
4.据权利要求1所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其中所述的包含不饱和脂肪基的多官能单体包括下列物质中的至少一个:
使用α,β-不饱和羧酸对多元醇进行酯化作用后得到的化合物,其是选自下列物质:二(甲基)丙烯酸乙二醇酯、含2~14环氧乙烷基团聚二甲基丙烯酸乙二醇酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三甲基丙烯酸季戊四醇酯、四甲基丙烯酸季戊四醇酯、含有2~14个环氧丙烷基团的二甲基丙烯酸丙二醇酯、五甲基丙烯酸双季戊四醇酯、六甲基丙烯酸双季戊四醇酯、以及三甲基丙烯酸双季戊四醇酯;
通过向具有缩水甘油基的化合物中加入(甲基)丙烯酸获得的化合物,其是选自下列物质:三羟甲基丙烷三缩水甘油醚丙烯酸加合物和双酚A二缩水甘油醚丙烯酸;
多聚羧酸的酯类化合物或多异氰酸酯与包含羟基与不饱和脂肪基的加合物,其是选自下列的物质:甲基丙烯酸-β-羟基乙酯β和甲基丙烯酸-β-羟基乙酯的甲苯二异氰酸酯加合物;和
甲基丙烯酸烷基酯,其是选自下列物质:甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯。
5.根据权利要求1所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其还包括:含有环氧或胺基的0.0001~3重量份的硅化合物。
6.根据权利要求5所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其中所述的包含环氧或胺基的硅化合物至少包括一个选自下列的物质:(3-缩水甘油醚基丙基)三甲氧基硅烷、(3-缩水甘油醚基丙基)三乙氧基硅烷、(3-缩水甘油醚基丙基)甲基二甲氧基硅烷、(3-缩水甘油醚基丙基)甲基二氧基硅烷、(3-缩水甘油醚基丙基)二甲基甲氧基硅烷、(3-缩水甘油醚基丙基)二甲基乙氧基硅烷、3,4-环氧丁基三甲氧基硅烷、3,4-环氧丁基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、2-(3,4-环氧环己基)乙基三乙氧基硅烷、以及氨基丙基三甲氧基硅烷。
7.根据权利要求1所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其还包括一种使粘度为2~30cps的溶剂。
8.根据权利要求7所述的用于高孔径LCD的有机绝缘层的负性抗蚀组合物,其中所述的溶剂至少包括一个选自下列的物质:乙酸乙酯、乙酸丁酯、二乙二醇二甲醚、二乙二醇二甲基乙基醚、甲氧基丙酸甲酯、乙氧基丙酸乙酯(EEP)、乳酸乙酯、丙二醇甲醚乙酸酯(PGMEA)、丙二醇甲醚、丙二醇丙醚、甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、二乙二醇甲醚醋酸酯、二乙二醇乙醚醋酸酯、丙酮、甲基异丁基酮、环己酮、二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)、γ-丁内酯、乙醚、乙二醇二甲醚、二甘醇二甲醚、四氢呋喃(THF)、甲醇、乙醇、丙醇、异丙醇、甲基溶纤剂、乙基溶纤剂、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、以及辛烷。
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CN101556434B (zh) * | 2008-04-07 | 2012-06-13 | 三养Ems株式会社 | 负性抗蚀剂组合物 |
CN104412208A (zh) * | 2012-07-06 | 2015-03-11 | 富士胶片株式会社 | 触摸面板用导电性膜以及触摸面板 |
CN106298797A (zh) * | 2015-05-21 | 2017-01-04 | 鸿富锦精密工业(深圳)有限公司 | 阵列基板的制作方法以及通过该方法制得的阵列基板 |
TWI810881B (zh) * | 2022-04-08 | 2023-08-01 | 新應材股份有限公司 | 感光性樹脂組成物以及硬化物 |
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JP2005338831A (ja) * | 2004-05-25 | 2005-12-08 | Samsung Electronics Co Ltd | 液晶表示装置の有機膜フォトレジスト組成物、そのスピンレスコーティング方法、これを用いた有機膜パターン形成方法及びこれにより製造された液晶表示装置 |
US20050279995A1 (en) | 2004-06-21 | 2005-12-22 | Samsung Electronics Co., Ltd. | Composition for preparing organic insulating film and organic insulating film prepared from the same |
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