WO2020113795A1 - 负性光刻胶及其应用 - Google Patents

负性光刻胶及其应用 Download PDF

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WO2020113795A1
WO2020113795A1 PCT/CN2019/072425 CN2019072425W WO2020113795A1 WO 2020113795 A1 WO2020113795 A1 WO 2020113795A1 CN 2019072425 W CN2019072425 W CN 2019072425W WO 2020113795 A1 WO2020113795 A1 WO 2020113795A1
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negative photoresist
additive
resin
silicon substrate
acrylic resin
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French (fr)
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李颖
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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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
    • 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
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the invention relates to the fields of photoresist resin, liquid crystal display and the like, in particular to a negative photoresist and its application.
  • Liquid crystal display is the most widely used real product in the market.
  • TFT-LCD as the core device of liquid crystal display, mainly includes three components: color film substrate, liquid crystal and array substrate.
  • the RGB color photoresist on the color film substrate respectively corresponds to the three sub-pixels on the array substrate, and the three sub-pixels are combined into one pixel.
  • the color display of the liquid crystal display is mainly realized by RGB three-color pixels on the color film substrate.
  • the RGB three-color pixels are formed by the photoresist of three different systems of RGB to form the pattern structure required by the design to assist color development.
  • COA Color Filter
  • Array technology is the technology of making color filter substrate on the array substrate.
  • RGB photoresist is coated on the array substrate.
  • the characteristics of the RGB photoresist will also affect the relevant characteristics of the array substrate.
  • Some new technologies also add a PFA photoresist after the RGB process in the COA process.
  • the RGB photoresist and PFA photoresist are mainly negative photoresists.
  • Negative photoresist is formed by adding photoinitiator, dispersion resin, pigment/dye, reactive monomer, etc. to the photoresist mixture, and forming a pattern by curing reaction under UV light, and the part without light is washed away by alkaline solution , Thereby forming a micro-morphology.
  • the negative photoresist used in TFT-LCD is mainly PFA photoresist and RGB photoresist.
  • RGB photoresist is mainly used for color development
  • PFA photoresist is mainly used for planarization and for replacing the silicon oxynitride layer.
  • the solution to the problem of photoresist peeling is mostly to improve the adhesion and crosslinking degree of the photoresist photocuring system.
  • the general method of improving adhesion is to use additives. This method has limited improvement and is easy to bring other side effects, such as high addition amount, and the risk of small molecule substances forming contaminants and contaminating the machine.
  • the incidence of peeling is extremely high, which requires some more efficient methods to improve the adhesion of materials to improve.
  • the technical solution for solving the above problems is to provide a negative photoresist containing catechol groups.
  • the composition of the negative photoresist includes 8%-9% of the resin matrix in mass percentage; modified resin, 1%-2%; dye, 5%-8%; Monomer, 5.8%-10.6%; photoinitiator, 0.1%-0.2%; first additive, 0.1%-0.2%; solvent, 70%-80%; wherein, the modified resin contains the o-benzene Diphenol group.
  • the composition of the negative photoresist includes, by mass percentage, the resin matrix, 9%-11%; dye, 5%-8%; monomer, 5%-11%; Photoinitiator, 0.1-0.2%; first additive, 0.1%-0.2%; second additive, 0.02%-0.2%; solvent, 70%-80%; wherein, the second additive contains the orthophthalic acid Phenol group.
  • the structural formula of the second additive is selected from at least one of the following structural formulas:
  • n, m, s and t in the structural formula of the second additive all represent the number of repeating units.
  • the molecular weight of the second additive is between 3000-9000.
  • the resin matrix has a double bond structure
  • the modified resin is formed by the resin matrix with a double bond structure and a small molecular substance with the catechol group passing through It is prepared by double bond addition reaction, wherein the structural formula of the small molecule substance is selected from at least one of the following structural formulas:
  • n 1-10.
  • the resin matrix is selected from at least one of pure acrylic resin, epoxy acrylic resin, polyester acrylic resin, unsaturated polyester, polyurethane acrylic resin, polyether acrylic resin, and acrylated polyphosphate One kind.
  • the photoinitiator includes at least one of initiator 369, initiator 379, nitroaniline, anthraquinone, benzophenone, and N-acetyl-4-nitronaphthylamine.
  • the monomer includes at least one of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, aliphatic hexafunctional polyurethane acrylate polymer, and ethoxylated pentaerythritol tetraacrylate.
  • the invention also provides an application of the negative photoresist, which is coated and cured on the surface of a silicon substrate to form a negative photoresist, the surface of the silicon substrate has a hydroxyl structure, and the negative photoresist It has a catechol group, and the hydroxyl structure in the catechol group forms a hydrogen bond structure with the hydroxyl structure of the silicon substrate.
  • the hydroxyl group in the catechol group and the hydroxyl group in the silicon substrate form hydrogen Bond to improve the adhesion between the negative photoresist formed by the negative photoresist and the silicon substrate; in the actual preparation process, compounds with catechol groups can be added directly to the formulation As a macromolecular additive, it can also react with the resin in the matrix to form a modified resin.
  • Modified resin or additives can be added according to the needs of the actual formula, and the flexibility of use is high; if used as an additive, the compound can be based on the benzene ring
  • the content of carbon atoms in the branched substituents adjusts the molecular weight to prevent the molecular weight from being too small to contaminate the machine; the size of the molecular weight does not affect its effect of improving adhesion.
  • the hydroxyl structure in the catechol group easily forms hydrogen bonds with the hydroxyl groups on the surface of the silicon substrate, and due to the high density of hydrogen bonds formed, if the silicon substrate is cleaned by ultraviolet lithography (EUV) The decrease in the hydroxyl group density will not significantly affect the overall adhesion of the substrate.
  • EUV ultraviolet lithography
  • FIG. 1 is a schematic diagram of the structure of a negative photoresist and a silicon substrate according to an embodiment of the present invention, which mainly reflects the hydrogen bond formed by the hydroxyl group on the silicon substrate and the hydroxyl group in the catechol group.
  • the negative photoresist of the present invention contains catechol groups.
  • the components in the negative photoresist include, by mass percentage, 8%-9% of the resin matrix; modified resin, 1%-2%; dye, 5%-8%; monomer, 5.8%-10.6% ; Photoinitiator, 0.1%-0.2%; first additive, 0.1%-0.2%; solvent, 70%-80%; wherein, the modified resin contains the catechol group.
  • the resin matrix is selected from at least one of pure acrylic resin, epoxy acrylic resin, polyester acrylic resin, unsaturated polyester, polyurethane acrylic resin, polyether acrylic resin, and acrylated polyphosphate.
  • the resin matrix has a double bond structure
  • the modified resin is prepared by a double bond addition reaction between the resin matrix having a double bond structure and a small molecular substance having the catechol group ,
  • the structural formula of the small molecule substance is selected from at least one of the following structural formulas:
  • n 1-10.
  • the resin matrix of the catechol group and the small molecule substance are subjected to an addition reaction to obtain the modified resin, and the modified resin is provided with a catechol group.
  • the photoinitiator includes at least one of initiator 369, initiator 379, nitroaniline, anthraquinone, benzophenone, and N-acetyl-4-nitronaphthylamine.
  • the monomer includes at least one of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, aliphatic hexafunctional polyurethane acrylate polymer, and ethoxylated pentaerythritol tetraacrylate.
  • the solvent may be one or more mixed solvents among propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, propylene glycol methyl ether (PM), and ethylene glycol ethyl ether acetate.
  • the first additive is an auxiliary agent, and may include a leveling agent and an antifoaming agent, wherein the mass of the leveling agent accounts for 0.05%-0.1% of the total mass of the negative photoresist resin composition, and the mass of the antifoaming agent accounts for 0.05%-0.1% of the total mass of the negative photoresist resin composition.
  • the components of the negative photoresist include, by mass percentage, the resin matrix, 9%-11%; dye, 5%-8%; monomer, 5%-11%; Photoinitiator, 0.1-0.2%; first additive, 0.1%-0.2%; second additive, 0.02%-0.2%; solvent, 70%-80%; wherein, the second additive contains the orthophthalic acid Phenol group.
  • the resin matrix is selected from at least one of pure acrylic resin, epoxy acrylic resin, polyester acrylic resin, unsaturated polyester, polyurethane acrylic resin, polyether acrylic resin, and acrylated polyphosphate.
  • the photoinitiator includes at least one of initiator 369, initiator 379, nitroaniline, anthraquinone, benzophenone, and N-acetyl-4-nitronaphthylamine.
  • the monomer includes at least one of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, aliphatic hexafunctional urethane acrylate polymer, and ethoxylated pentaerythritol tetraacrylate.
  • the solvent may be one or more mixed solvents among propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, propylene glycol methyl ether (PM), and ethylene glycol ethyl ether acetate.
  • the first additive is an auxiliary agent, and may include a leveling agent and an antifoaming agent, wherein the mass of the leveling agent accounts for 0.05%-0.1% of the total mass of the negative photoresist resin composition, and the mass of the antifoaming agent accounts for 0.05%-0.1% of the total mass of the negative photoresist resin composition.
  • the structural formula of the second additive is at least one selected from the following structural formulas:
  • n, m, s and t in the structural formula of the second additive all represent the number of repeating units.
  • the molecular weight of the second additive is between 3000-9000.
  • the second additive with the catechol group is directly added as an auxiliary agent to the other components of the negative photoresist.
  • the compound with the catechol group is used as the second additive.
  • the compound may be a repeating unit according to the carbon content of the substituents of the benzene ring branch, ie, n, m, s, and t Number to adjust the molecular weight to prevent the molecular weight from being too small to form contaminants to contaminate the machine; the size of the molecular weight does not affect its effect of improving adhesion.
  • the invention also provides an application of the negative photoresist.
  • the negative photoresist in the above two embodiments is coated and cured on the surface of a silicon substrate to form a negative photoresist 2.
  • the silicon substrate The surface of 1 has a hydroxyl structure, and the negative photoresist has a catechol group.
  • the hydroxyl structure in the catechol group and the hydroxyl structure of the silicon substrate 1 form a hydrogen bond structure.
  • the hydroxyl structure in the catechol group easily forms hydrogen bonds with the hydroxyl groups on the surface of the silicon substrate 1, and due to the higher density of hydrogen bonds formed, if the silicon substrate 1 is subjected to ultraviolet lithography ( EUV)
  • EUV ultraviolet lithography
  • the density of hydroxyl groups after cleaning will not significantly affect the overall adhesion of the substrate.
  • the silicon substrate 1 may be a silicon oxide substrate or a silicon nitride substrate.
  • the negative photoresist of the present invention has a wide range of applications.
  • the corresponding device in a liquid crystal display includes a COA array substrate or a color filter substrate.
  • it can also be applied to other negative photoresists. Structural device.

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Abstract

一种负性光刻胶及其应用，负性光刻胶含有邻苯二酚基团。负性光刻胶涂覆并固化于硅基底(1)的表面形成负性光阻(2)，硅基底(1)的表面具有羟基结构，负性光刻胶具有邻苯二酚基团，邻苯二酚基团中的羟基结构与硅基底(1)的羟基结构之间形成氢键结构。通过在负性光刻胶内加入带有邻苯二酚基团的化合物，使得邻苯二酚基团中的羟基与硅基底(1)中的羟基形成氢键，以提高由负性光刻胶形成的负性光阻(2)与硅基底(1)之间的粘附力。

Description

负性光刻胶及其应用 技术领域
本发明涉及光刻胶树脂、液晶显示器等领域，具体为一种负性光刻胶及其应用。
背景技术
液晶显示器(LCD)是目前市场中应用最广泛的现实产品。而TFT-LCD作为液晶显示器最核心的器件，它主要包括彩膜基板、液晶、阵列基板三个组成部分。彩膜基板上的RGB彩色光刻胶分别对应阵列基板上的三个子像素，三个子像素合成一个像素。液晶显示器的色彩显示主要是依靠彩膜基板上RGB三色像素点实现的。RGB三色像素点则是通过RGB三种不同体系的光阻成膜，形成设计需求的图案结构，以协助显色的。
COA(Color Filter Array)技术，是将彩膜基板制作在阵列基板上的技术，RGB光刻胶是涂布在阵列基板上的，RGB光刻胶的特性也会影响到阵列基板的相关特性。有些新技术中也会在COA制程中的RGB制程后加一道PFA光刻胶，RGB光刻胶以及PFA光刻胶主要都是负性光阻。
负性光阻是在光阻混合物中加入光引发剂、分散树脂、颜料/染料、反应性单体等，并通过UV光照下进行固化反应而形成图案的，无光照部分则被碱液洗掉，从而形成微观形貌的。通常TFT-LCD中使用的负性光阻主要是PFA光 刻胶、RGB光刻胶。RGB光刻胶主要是显色用的，而PFA光刻胶则主要起到平坦化以及起到代替氮氧化硅层的作用。在负性光阻达到一定厚度时，在光固化反应过程中，由于光刻胶与基底底层黏附力较小，容易产生剥落(光刻胶图案局部位置发生剥落)；或者当前制程膜层特性或者基板清洗条件变化时，基板表面有机官能团数量及种类发生变化，负性光刻胶与基板的附着力特性发生变化时，也容易产生负性光阻剥落；这种RGB光阻的缺失形成会造成开口区域漏光，更严重的甚至导致COA阵列基板底层金属裸漏，造成电性方面失常或短路，影响整个面板的显示品质甚至显示不良等问题。若是PFA光刻胶弯折，则及易造成RGB光刻胶裸漏在外，除气工艺中产生风险也及大，也可能产生其他电性方面的不良影响。当前制程上或者光刻胶配方上对于光刻胶剥落这一问题的解决方法，大多是提高光刻胶光固化体系的黏附力以及交联程度。普遍提高黏附力的方法都是使用添加剂，这种方法改善力度有限并且及易带来其他副作用，如添加量高，小分子物质有形成升化物污染机台的风险等。对于一些特殊的像素设计，剥落发生率极高，这就需要有一些更高效的提高材料黏附力的方法来改善。
技术问题
为了解决上述技术问题：提供一种负性光刻胶及其应 用，通过在负性光刻胶内加入带有邻苯二酚基团的化合物，使得邻苯二酚基团中的羟基与硅基底中的羟基形成氢键，以提高由负性光刻胶形成的负性光阻与硅基底之间的粘附力。
技术解决方案
解决上述问题的技术方案是：提供了一种负性光刻胶，含有邻苯二酚基团。
在本发明一实施例中，所述的负性光刻胶，其组分按质量百分比包括树脂基体8％-9％；改性树脂，1％-2％；染料，5％-8％；单体，5.8％-10.6％；光引发剂，0.1％-0.2％；第一添加剂，0.1％-0.2％；溶剂，70％-80％；其中，所述改性树脂中含有所述邻苯二酚基团。
在本发明一实施例中，所述的负性光刻胶，其组分按质量百分比包括树脂基体，9％-11％；染料，5％-8％；单体，5％-11％；光引发剂，0.1-0.2％；第一添加剂，0.1％-0.2％；第二添加剂，0.02％-0.2％；溶剂，70％-80％；其中，所述第二添加剂含有所述邻苯二酚基团。
在本发明一实施例中，所述第二添加剂的结构式选自以下结构式中的至少一种：
Figure PCTCN2019072425-appb-000001
Figure PCTCN2019072425-appb-000002
其中，所述第二添加剂的结构式中n、m、s、t均表示重复单元个数。
在本发明一实施例中，所述第二添加剂的分子量在3000-9000之间。
在本发明一实施例中，所述树脂基体带有双键结构，所述改性树脂为带有双键结构的所述树脂基体与带有所述邻苯二酚基团的小分子物质通过双键加成反应制备而成，其中所述小分子物质的结构式选自以下结构式中的至少一种：
Figure PCTCN2019072425-appb-000003
所述小分子物质的结构式中，n为1-10。
在本发明一实施例中，所述树脂基体选自纯丙烯酸树脂，环氧丙烯酸树脂，聚酯丙烯酸树脂，不饱和聚酯，聚 氨酯丙烯酸树脂，聚醚丙烯酸树脂，丙烯酸化聚磷酸酯中的至少一种。
在本发明一实施例中，所述光引发剂包括引发剂369、引发剂379、硝基苯胺、蒽醌、二苯甲酮、N-乙酰-4-硝基萘胺中的至少一种。
在本发明一实施例中，所述单体包括二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯聚合物、乙氧化季戊四醇四丙烯酸酯中的至少一种。
本发明还提供了一种所述负性光刻胶的应用，其涂覆并固化于硅基底的表面形成负性光阻，所述硅基底的表面具有羟基结构，所述负性光刻胶具有邻苯二酚基团，所述邻苯二酚基团中的羟基结构与所述硅基底的羟基结构之间形成氢键结构。
有益效果
本发明的负性光刻胶及其应用，通过在负性光刻胶内加入带有邻苯二酚基团的化合物，使得邻苯二酚基团中的羟基与硅基底中的羟基形成氢键，以提高由负性光刻胶形成的负性光阻与硅基底之间的粘附力；在实际的制备过程中，可以将带有邻苯二酚基团的化合物直接添加进配方中作为大分子添加剂，又可以与基体中的树脂反应，形成改性树脂，可根据实际配方的需求选择添加改性树脂或添加 剂，使用灵活度较高；若作为添加剂使用，该化合物可根据苯环支链的取代基碳原子含量调节分子量，避免分子量过小形成升化物污染机台；分子量的大小并不影响其提高附着力的效果。邻苯二酚基团中的羟基结构极易与所述硅基底表面的羟基形成氢键，并且，由于形成的氢键密度较高，若所述硅基底在经紫外光刻(EUV)清洗后羟基密度降低，也不会对基板整体黏附力的效果产生明显的影响。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
下面结合附图和实施例对本发明作进一步解释。
图1是本发明实施例的负性光阻与硅基底的结构示意图，主要体现硅基底上的羟基与所述邻苯二酚基团中的羟基形成的氢键。
1硅基底；          2负性光阻。
本发明的实施方式
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明， 而不能理解为对本发明的限制。
以下实施例的说明是参考附加的图式，用以例示本发明可用以实施的特定实施例。本发明所提到的方向用语，例如「上」、「下」、「前」、「后」、「左」、「右」、「顶」、「底」等，仅是参考附加图式的方向。因此，使用的方向用语是用以说明及理解本发明，而非用以限制本发明。
在一实施例中，本发明的负性光刻胶，含有邻苯二酚基团。所述的负性光刻胶中的组分按质量百分比包括树脂基体8％-9％；改性树脂，1％-2％；染料，5％-8％；单体，5.8％-10.6％；光引发剂，0.1％-0.2％；第一添加剂，0.1％-0.2％；溶剂，70％-80％；其中，所述改性树脂中含有所述邻苯二酚基团。
所述树脂基体选自纯丙烯酸树脂，环氧丙烯酸树脂，聚酯丙烯酸树脂，不饱和聚酯，聚氨酯丙烯酸树脂，聚醚丙烯酸树脂，丙烯酸化聚磷酸酯中的至少一种。
所述树脂基体带有双键结构，所述改性树脂为带有双键结构的所述树脂基体与带有所述邻苯二酚基团的小分子物质通过双键加成反应制备而成，其中所述小分子物质的结构式选自以下结构式中的至少一种：
Figure PCTCN2019072425-appb-000004
所述小分子物质的结构式中，n为1-10。
本实施例中，将邻苯二酚基团的所述树脂基体与所述小分子物质进行加成反应，得到所述改性树脂，使改性树脂具备邻苯二酚基团。
所述光引发剂包括引发剂369、引发剂379、硝基苯胺、蒽醌、二苯甲酮、N-乙酰-4-硝基萘胺中的至少一种。
所述单体包括二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯聚合物、乙氧化季戊四醇四丙烯酸酯中的至少一种。
所述溶剂可以为丙二醇甲醚醋酸酯、3-乙氧基丙酸乙酯、丙二醇甲醚(PM)、乙酸乙二醇乙醚中一种或几种混合溶剂。
所述第一添加剂为助剂，可以包括流平剂和消泡剂，其中，流平剂的质量占负性光刻胶树脂组合物总质量的0.05％-0.1％，消泡剂的质量占负性光刻胶树脂组合物总质量的0.05％-0.1％。
在本发明另一实施例中，所述的负性光刻胶的组分按质量百分比包括树脂基体，9％-11％；染料，5％-8％；单体，5％-11％；光引发剂，0.1-0.2％；第一添加剂，0.1％-0.2％；第二添加剂，0.02％-0.2％；溶剂，70％-80％；其中，所述第二添加剂含有所述邻苯二酚基团。
所述树脂基体选自纯丙烯酸树脂，环氧丙烯酸树脂，聚酯丙烯酸树脂，不饱和聚酯，聚氨酯丙烯酸树脂，聚醚丙烯酸树脂，丙烯酸化聚磷酸酯中的至少一种。
所述光引发剂包括引发剂369、引发剂379、硝基苯胺、蒽醌、二苯甲酮、N-乙酰-4-硝基萘胺中的至少一种。
所述单体包括二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯聚合物、乙氧化季戊四醇四丙烯酸酯中的至少一种。
所述溶剂可以为丙二醇甲醚醋酸酯、3-乙氧基丙酸乙酯、丙二醇甲醚(PM)、乙酸乙二醇乙醚中一种或几种混合溶剂。
所述第一添加剂为助剂，可以包括流平剂和消泡剂，其中，流平剂的质量占负性光刻胶树脂组合物总质量的0.05％-0.1％，消泡剂的质量占负性光刻胶树脂组合物总质量的0.05％-0.1％。
所述第二添加剂的结构式选自以下结构式中的至少一种：
Figure PCTCN2019072425-appb-000005
其中，所述第二添加剂的结构式中n、m、s、t均表示重复单元个数。所述第二添加剂的分子量在3000-9000之间。本实施例中，将带有所述邻苯二酚基团的第二添加剂直接作为助剂加入所述的负性光刻胶的其他组分中。本实施例中，带有所述邻苯二酚基团的化合物作为第二添加剂使用，该化合物可根据苯环支链的取代基碳原子含量, 即n、m、s、t均表示重复单元个数，来调节分子量，避免分子量过小形成升化物污染机台；分子量的大小并不影响其提高附着力的效果。
本发明还提供了一种所述负性光刻胶的应用，将上述两个实施例中的负性光刻胶涂覆并固化于硅基底的表面形成负性光阻2，所述硅基底1的表面具有羟基结构，所述负性光刻胶具有邻苯二酚基团，所述邻苯二酚基团中的羟基结构与所述硅基底1的羟基结构之间形成氢键结构。所述邻苯二酚基团中的羟基结构极易与所述硅基底1表面的羟基形成氢键，并且，由于形成的氢键密度较高，若所述硅基底1在经紫外光刻(EUV)清洗后羟基密度降低，也不会对基板整体黏附力的效果产生明显的影响。本实施例中，所述硅基底1可以采用氧化硅基底或者氮化硅基底。
本发明的所述负性光刻胶的应用范围广泛，如在液晶显示器中的对应的器件中，包括COA阵列基板上，或者彩膜基板上，当然还可以应用在其他需要采用负性光阻的结构器件中。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种负性光刻胶，其含有邻苯二酚基团。
  2. 根据权利要求1所述的负性光刻胶，其组分按质量百分比包括
    Figure PCTCN2019072425-appb-100001
    其中，所述改性树脂中含有所述邻苯二酚基团。
  3. 根据权利要求1所述的负性光刻胶，其组分按质量百分比包括
    Figure PCTCN2019072425-appb-100002
    其中，所述第二添加剂含有所述邻苯二酚基团。
  4. 根据权利要求3所述的负性光刻胶，其中，所述第二添加剂的结构式选自以下结构式中的至少一种：
    Figure PCTCN2019072425-appb-100003
    其中，所述第二添加剂的结构式中n、m、s、t均表示重复单元个数。
  5. 根据权利要求4所述的负性光刻胶，其中，所述第二添加剂的分子量在3000-9000之间。
  6. 根据权利要求3所述的负性光刻胶，其中，所述树脂基体带有双键结构，所述改性树脂为带有双键结构的所述树脂基体与带有所述邻苯二酚基团的小分子物质通过双键加成反应制备而成，其中所述小分子物质的结构式选自以下结构式中的至少一种：
    Figure PCTCN2019072425-appb-100004
    所述小分子物质的结构式中，n为1-10。
  7. 根据权利要求2或3所述的负性光刻胶，其中，所述树脂基体选自纯丙烯酸树脂，环氧丙烯酸树脂，聚酯丙烯酸树脂，不饱和聚酯， 聚氨酯丙烯酸树脂，聚醚丙烯酸树脂，丙烯酸化聚磷酸酯中的至少一种。
  8. 根据权利要求2或3所述的负性光刻胶，其中，所述光引发剂包括引发剂369、引发剂379、硝基苯胺、蒽醌、二苯甲酮、N-乙酰-4-硝基萘胺中的至少一种。
  9. 根据权利要求2或3所述的负性光刻胶，其中，所述单体包括二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯聚合物、乙氧化季戊四醇四丙烯酸酯中的至少一种。
  10. 一种所述负性光刻胶的应用，其中，所述负性光刻胶涂覆并固化于硅基底的表面形成负性光阻，所述硅基底的表面具有羟基结构，所述负性光刻胶具有邻苯二酚基团，所述邻苯二酚基团中的羟基结构与所述硅基底的羟基结构之间形成氢键结构。
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