WO2020051939A1 - 光刻胶组合物及彩色滤光片 - Google Patents

光刻胶组合物及彩色滤光片 Download PDF

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WO2020051939A1
WO2020051939A1 PCT/CN2018/106598 CN2018106598W WO2020051939A1 WO 2020051939 A1 WO2020051939 A1 WO 2020051939A1 CN 2018106598 W CN2018106598 W CN 2018106598W WO 2020051939 A1 WO2020051939 A1 WO 2020051939A1
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Prior art keywords
photoresist composition
weight
parts
derivative
acrylic resin
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PCT/CN2018/106598
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English (en)
French (fr)
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李颖
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深圳市华星光电技术有限公司
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Publication of WO2020051939A1 publication Critical patent/WO2020051939A1/zh

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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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

Definitions

  • the invention relates to the technical field of liquid crystal display panels, in particular to a photoresist composition and a color filter.
  • a thin film transistor liquid crystal display mainly includes three components: a color filter (CF) substrate, a liquid crystal, and a thin film transistor (TFT) substrate.
  • the three red, green, and blue (ie, RGB) pixel points on the CF substrate correspond to three sub-pixels on the thin-film transistor substrate, and the three sub-pixels are combined into one pixel.
  • the color display of the liquid crystal display is mainly realized by the RGB three-color pixels on the color filter 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, and then assist to display the color.
  • RGB negative photoresist is made by adding a photoinitiator, a dispersing resin, a pigment / dye (colorant), a reactive monomer, etc. to a photoresist mixture, and curing the reaction under ultraviolet (UV) light. Form a pattern.
  • UV light ultraviolet
  • the film thickness of the RGB negative photoresist reaches a certain thickness, during the photocuring reaction, the reaction degree between the bottom layer and the surface layer is inconsistent, and problems such as peeling of the photoresist are likely to occur.
  • the above problem of photoresist peeling can be overcome by improving the adhesion between the photoresist material and the substrate. In general, adhesion can be improved by increasing the degree of reaction of the underlying layer and the degree of hardening.
  • the ultra-violet (EUV) or deep ultraviolet (DUV) cleaning process is performed before the RGB coating.
  • EUV ultra-violet
  • DUV deep ultraviolet
  • an active oxygen atom can be consumed by adding an oxygen polymerization inhibitor substance to the photoresist composition
  • the reaction efficiency of the photoresist composition can be improved.
  • a color photoresist composition with a high color gamut or a high color concentration since the content of pigment or dye is relatively high, the way of adding an oxygen polymerization inhibitor substance will make other color photoresist compositions The proportion of material components is limited.
  • the present invention provides a photoresist composition and a color filter, which can solve other material components in the color photoresist composition in a manner that solves the problem of adding an oxygen polymerization inhibitor substance in the prior art.
  • An object of the present invention is to provide a photoresist composition and a color filter.
  • the photoresist composition is protected from active oxygen atoms by adding a small amount of a cationic photoinitiator, thereby improving photolithography.
  • the adhesion between the adhesive composition and the substrate is applicable to a color photoresist composition having a high color gamut or a high color density.
  • an embodiment of the present invention provides a photoresist composition, wherein the photoresist composition includes: 4 to 10 parts by weight of a resin matrix; 5 to 8 parts by weight of a colorant; Greater than 0 and less than or equal to 5 parts by weight of a radically polymerizable monomer; greater than 0 and less than or equal to 0.2 parts by weight of a radical photoinitiator; greater than 0 and less than or equal to 0.002 parts by weight of a cationic photoinitiator, wherein The cationic photoinitiator has a maximum absorption wavelength between 280 and 400 nanometers, and the cationic photoinitiator is selected from the group consisting of diaryl iodonium salts and derivatives thereof; 70 to 80 parts by weight A solvent; and 0.1 to 0.2 parts by weight of an additive.
  • the derivative of the diaryl iodonium salt is selected from a group consisting of:
  • R 1 is C n H 2n + 1 , OC n H 2n + 1 , C (CH 3 ) 3 or NO 2 , where 8 ⁇ n ⁇ 20;
  • X - is BF 4 -, PF 6 -, SbF 6 - or AsF 6 -.
  • the resin matrix includes at least one of an acrylic resin and a derivative thereof.
  • the derivative of the acrylic resin includes at least one of epoxy acrylic resin, urethane acrylic resin, polyester acrylic resin, and polyether acrylic resin.
  • the colorant includes azos, quinacridones, actinides, titanines, anthraquinones, anthraquinone derivatives, pyridopyridine diones , At least one of a pyridopyridine dione derivative, a triarylmethane derivative, and a triarylmethane derivative.
  • the free radical polymerization monomer includes alkyl acrylate, hydroxy acrylate, vinyl reactive diluent, ethylene glycol diacrylate, propylene glycol diacrylate, and glycol diacrylate. At least one of an acrylate, an alkoxylated acrylate, a vinyl ether acrylate, a methacrylic acid phosphate, a heterocyclic or benzene ring-containing acrylate, and an active amine-containing acrylate.
  • the free radical photoinitiator includes at least one of thiaxanthone, thiaxanthone derivative, benzophenone, and benzophenone derivative.
  • another embodiment of the present invention provides a photoresist composition, wherein the photoresist composition includes: 4 to 10 parts by weight of a resin matrix; 5 to 8 parts by weight of a colorant; greater than 0 and less than Or equal to 5 parts by weight of a radical polymerizable monomer; greater than 0 and less than or equal to 0.2 parts by weight of a radical photoinitiator; greater than 0 and less than or equal to 0.002 parts by weight of a cationic photoinitiator, wherein the cationic photoinitiator
  • the maximum absorption wavelength is between 280 and 400 nanometers; and 70 to 80 parts by weight of the solvent.
  • the cationic photoinitiator is selected from the group consisting of diaryl iodonium salts and derivatives thereof.
  • the derivative of the diaryl iodonium salt is selected from a group consisting of:
  • R 1 is C n H 2n + 1 , OC n H 2n + 1 , C (CH 3 ) 3 or NO 2 , where 8 ⁇ n ⁇ 20;
  • X - is BF 4 -, PF 6 -, SbF 6 - or AsF 6 -.
  • the resin matrix includes at least one of an acrylic resin and a derivative thereof.
  • the derivative of the acrylic resin includes at least one of epoxy acrylic resin, urethane acrylic resin, polyester acrylic resin, and polyether acrylic resin.
  • the colorant includes azos, quinacridones, actinides, titanines, anthraquinones, anthraquinone derivatives, pyridopyridine diones , At least one of a pyridopyridine dione derivative, a triarylmethane derivative, and a triarylmethane derivative.
  • the free radical polymerization monomer includes alkyl acrylate, hydroxy acrylate, vinyl reactive diluent, ethylene glycol diacrylate, propylene glycol diacrylate, and glycol diacrylate. At least one of an acrylate, an alkoxylated acrylate, a vinyl ether acrylate, a methacrylic acid phosphate, a heterocyclic or benzene ring-containing acrylate, and an active amine-containing acrylate.
  • the free radical photoinitiator includes at least one of thiaxanthone, thiaxanthone derivative, benzophenone, and benzophenone derivative.
  • the photoresist composition further includes an additive in an amount of 0.1 to 0.2 parts by weight.
  • another technical solution adopted by the present invention is to provide a color filter, wherein the color filter is coated with any one of the photoresist compositions described above.
  • the photoresist composition and color filter of the present invention are not affected by active oxygen atoms, thereby improving the adhesion between the photoresist composition and the substrate, and can be applied to high color Domain or high color density color photoresist composition.
  • An embodiment of the present invention provides a photoresist composition.
  • the photoresist composition includes: 4 to 10 parts by weight of a resin matrix; 5 to 8 parts by weight of a colorant (also referred to as a pigment or a dye); 0 and less than or equal to 5 parts by weight of a radical polymerizable monomer; more than 0 and less than or equal to 0.2 parts by weight of a radical photoinitiator; and more than 0 and less than or equal to 0.002 parts by weight of a cationic photoinitiator, wherein the cations
  • the maximum absorption wavelength of the photoinitiator is between 280 and 400 nanometers; and 70 to 80 parts by weight of the solvent.
  • the resin matrix includes at least one of an acrylic resin and a derivative thereof.
  • the derivative of the acrylic resin includes at least one of epoxy acrylic resin, urethane acrylic resin, polyester acrylic resin, and polyether acrylic resin.
  • the colorant includes azos, quinacridones, actinides, titanium cyanines, anthraquinones, anthraquinone derivatives, pyridopyridine diones (DPPs ), At least one of pyridopyridine dione derivatives, triarylmethanes, and triarylmethanes.
  • the index number corresponding to the azo pigment includes R144, R37, R38, R41, R111, Y12, Y16 or Y17.
  • the index number corresponding to the quinacridone includes Y138, R209, V19, PR122, or PR202.
  • the index numbers corresponding to the actinides include R178, R179, R190, R244, R123, R149, and V29.
  • the index numbers corresponding to the titanium cyanines include G58, G59, G63, G7, G36, B15, B15: 1, B15: 3, B15: 4, B15: 6 or B16; the anthraquinone
  • the index number corresponding to the class includes R177, R83, R168, R216, R226, B21, B22, B60, B64, B65, Y23, or Y147;
  • the index number corresponding to the pyridopyridine dione class includes R254, R255, R264 Or R272;
  • the corresponding index numbers of the triarylmethanes include B18, B19, B56, B61, B62, V3, V27, V39, R169, R81: 1, or R81: 2.
  • the radical polymerizable monomer includes alkyl acrylate, hydroxy acrylate, vinyl reactive diluent, ethylene glycol diacrylate, propylene glycol diacrylate, glycol diacrylate, At least one of an alkoxylated acrylate, a vinyl ether acrylate, a methacrylic acid phosphate, a heterocyclic or benzene ring-containing acrylate, and an active amine-containing acrylate.
  • the cationic photoinitiator is selected from the group consisting of diaryl iodonium salts and derivatives thereof. It should be mentioned here that the diaryl iodonium salt and its derivative can not only initiate cationic polymerization but also radical polymerization after photodecomposition reaction, so they have higher photoinitiation efficiency.
  • the structural formula of the diaryl iodonium salt is as shown in the following formula (1).
  • the derivative of the diaryl iodonium salt is selected from a group consisting of the following, as shown in formulas (2) to (4):
  • R 1 is C n H 2n + 1 , OC n H 2n + 1 , C (CH 3 ) 3 or NO 2 , where 8 ⁇ n ⁇ 20;
  • X - is BF 4 -, PF 6 -, SbF 6 - or AsF 6 -.
  • the derivative of the diaryl iodonium salt is, for example, a modified product of the diaryl iodonium salt for the purpose of increasing the maximum absorption wavelength.
  • the diaryl iodonium salt (formula (1)) has a maximum absorption wave of approximately 280 nm, the light absorption rate is not high. Therefore, the derivative of the diaryl iodonium salt (formula (2)) can be modified (for example, by attaching an aryl ketone group having a higher light energy absorption rate to the diaryl iodonium salt).
  • the maximum absorption wavelength to the formula (4)) is higher than the diaryl iodonium salt.
  • the maximum absorption wavelength of the derivative of the diaryl iodonium salt according to formula (2) is approximately 250-300 nm. In another embodiment, the maximum absorption wavelength of the derivative of the diaryl iodonium salt according to formula (3) is approximately 335 nanometers. In yet another embodiment, the maximum absorption wavelength of the derivative of the diaryl iodonium salt according to formula (4) is approximately 296 or 336 nanometers.
  • n is preferably between 8 and 20.
  • the value of n is, for example, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19.
  • the free radical photoinitiator comprises at least one of thiaxanthone, thiaxanthone derivative, benzophenone and benzophenone derivative.
  • the free radical initiator can be used to broaden the light absorption wavelength range (eg, increase the maximum light absorption wavelength) of the cationic photoinitiator (such as a diaryl iodonium salt or a derivative thereof). After the radical initiator absorbs light energy, electrons can be transferred to the cationic photoinitiator (such as a diaryl iodonium salt or a derivative thereof), thereby generating a super acid.
  • the super strong acid can initiate a cationic polymerization reaction and a radical polymerization reaction.
  • the diaryl iodonium salt has a structure of formula (5) to formula (7). Strong acid, simultaneously initiates cationic polymerization and free radical polymerization.
  • SbF 6 - may also be replaced with BF 4 -, PF 6 - or AsF 6 -.
  • the structures of the formulas (5) to (7) contain an alkane chain structure having a branched chain with a number of C atoms greater than 8, which can increase the solubility of the initiator in the system and reduce toxicity.
  • the photoresist composition further includes an additive in an amount of 0.1 to 0.2 parts by weight.
  • the additive includes at least one of a wetting and dispersing agent, a leveling agent, and a polymerization inhibitor.
  • the color filter includes: a substrate; a black matrix disposed on the substrate; and a color filter layer disposed on the black matrix.
  • the color filter layer is provided by an embodiment of the present invention.
  • a photoresist composition is formed. Further, the photoresist composition is coated on each film layer of the color filter, and the photoresist composition is not affected by active oxygen atoms, thereby improving the space between the photoresist composition and the substrate.
  • the adhesive force can improve the yield of the color filter.
  • the photoresist composition of the present invention and the color filter using the same are related to a cationic photocuring system and have the following advantages.
  • the method of adding a diaryl iodonium salt as a cationic photoinitiator is applicable to current high-color-concentration photoresist materials. Because the amount of cationic photoinitiator is small (for example, about greater than 0 and less than or equal to 0.002 weight percent) ), And no additional cationic monomer is needed, so the problem of limiting the proportion of other material components does not arise.
  • the photoresist composition of the embodiment of the present invention is based on the original formula, and a part of the radical photoinitiator is replaced with a cationic photoinitiator, so it does not affect the photocuring characteristics of the original system, and can be free from the original Based curing systems (such as acrylic resins) have better compatibility.
  • cationic photoinitiators can initiate cationic polymerization as well as radical polymerization at the same time, and have higher initiation efficiency.
  • the cationic photoinitiator is not affected by active oxygen on the surface of the substrate, does not cause oxygen inhibition and initiator deactivation, and has a small curing shrinkage rate, which is conducive to increasing the adhesion of the photoresist composition to the substrate.
  • This cationic photo-curing system has good deep-layer curability, so it can reduce or avoid the risk of photoresist peeling.
  • the photoresist composition involving a cation-initiated system has a smaller volume shrinkage (relative to a radical-initiated system) and has the characteristics of post-curing after the photocuring reaction, further strengthening the photoresist combination ⁇ ⁇ ⁇ ⁇ Object hardenability.

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Abstract

一种光刻胶组合物及彩色滤光片，其中光刻胶组合物包含︰4至10重量份的树脂基体；5至8重量份的着色剂；大于0且小于或等于5重量份的自由基聚合单体；大于0且小于或等于0.2重量份的自由基光引发剂；大于0且小于或等于0.002重量份的阳离子光引发剂，其中阳离子光引发剂的最大吸收波长介于280至400纳米之间；及70至80重量份的溶剂。光刻胶组合物不受活性氧原子的影响，有利于提升光刻胶组合物与基板之间的附着力，并且适用于高色域或者高色浓度的彩色光刻胶组合物。

Description

光刻胶组合物及彩色滤光片 技术领域
本发明涉及液晶显示面板技术领域，尤其涉及一种光刻胶组合物及彩色滤光片。
背景技术
液晶显示器(liquid crystal display，LCD)是目前市场中应用最广泛的现实产品。例如，薄膜晶体管液晶显示器(thin film transistor liquid crystal display，TFT-LCD)主要包括彩色滤光片(color filter，CF)基板、液晶、薄膜晶体管(Thin Film Transistor，TFT)基板三个组成部分。CF基板上的红、绿、蓝(即RGB)三色像素点分别对应薄膜晶体管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色滤光片基板上RGB三色像素点实现的。RGB三色像素点则是通过RGB三种不同体系的光刻胶成膜形成设计需求的图案结构，进而完成协助显示颜色。
RGB负性光刻胶(photoresist)是在光刻胶混合物中加入光引发剂、分散树脂、颜料/染料(着色剂)、反应性单体等，并通过紫外线(UV)光照下进行固化反应而形成图案。在RGB负性光刻胶的膜厚达到一定厚度时，在光固化反应过程中，底层与表层反应程度不一致，容易产生光刻胶剥落(peeling)等问题。上述光刻胶剥落的问题，可通过提升光刻胶材料与基板之间的附着力来克服。一般而言，可通过提高底层反应程度及硬化度来提高附着力。但是，在实际制程中，RGB涂布之前会进行超紫外光(EUV)或者深紫外光(DUV)的清洗过程。这个清洗过程中会产生一些活性氧原子，这些活性氧原子会对自由基聚合的引发剂产生影响，造成引发剂失去活性，而无法提高附着力。
对于上述问题，虽然可通过在光刻胶组合物中添加氧阻聚剂类物质来消耗活性氧原子，从而提高光刻胶组合物的反应效率。然而，对于高色域或者 高色浓度的彩色光刻胶组合物而言，由于颜料或者染料成分含量较高，所以添加氧阻聚剂类物质的方式会使得彩色光刻胶组合物中的其他材料成分的比例受到限制。
故，有必要提供一种光刻胶组合物及彩色滤光片，以解决现有技术所存在的问题。
发明内容
有鉴于此，本发明提供一种光刻胶组合物及彩色滤光片，以解决现有技术所存在的添加氧阻聚剂类物质的方式会使得彩色光刻胶组合物中的其他材料成分的比例受到限制的问题。
本发明的一目的在于提供一种光刻胶组合物及彩色滤光片，其是通过加入少量的阳离子光引发剂，以使光刻胶组合物不受活性氧原子的影响，进而提升光刻胶组合物与基板之间的附着力，并且可适用于高色域或者高色浓度的彩色光刻胶组合物。
为达成本发明的前述目的，本发明一实施例提供一种光刻胶组合物，其中所述光刻胶组合物包含：4至10重量份的树脂基体；5至8重量份的着色剂；大于0且小于或等于5重量份的自由基聚合单体；大于0且小于或等于0.2重量份的自由基光引发剂；大于0且小于或等于0.002重量份的阳离子光引发剂，其中所述阳离子光引发剂的最大吸收波长在介于280至400纳米之间，以及所述阳离子光引发剂选自于二芳基碘鎓盐及其衍生物所组成的一族群；70至80重量份的溶剂；及0.1至0.2重量份的添加剂。
在本发明的一实施例中，所述二芳基碘鎓盐的衍生物是由下列所组成的一族群所选出：
Figure PCTCN2018106598-appb-000001
Figure PCTCN2018106598-appb-000002
及
Figure PCTCN2018106598-appb-000003
其中：
R 1是C nH 2n+1、OC nH 2n+1、C(CH 3) 3或NO 2，其中8<n<20；及
X －是BF 4 －、PF 6 －、SbF 6 －或AsF 6 －。
在本发明的一实施例中，所述树脂基体中包含有丙烯酸树脂及其衍生物中的至少一种。
在本发明的一实施例中，所述丙烯酸树脂的衍生物包含环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂及聚醚丙烯酸树脂中的至少一种。
在本发明的一实施例中，所述着色剂包含偶氮类、喹吖啶酮类、苝系类、钛菁类、蒽醌类、蒽醌类衍生物、吡喏并吡喏二酮类、吡喏并吡喏二酮类衍生物、三芳甲烷类以及三芳甲烷类衍生物中的至少一种。
在本发明的一实施例中，所述自由基聚合单体包含丙烯酸烷基酯、丙烯酸羟基酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、二醇类二丙烯酸酯、烷氧基化丙烯酸酯、乙烯基醚类丙烯酸酯、甲基丙烯酸磷酸酯、含有杂环或苯环的丙烯酸酯以及含有活性胺的丙烯酸酯中的至少一种。
在本发明的一实施例中，所述自由基光引发剂包含硫杂蒽酮、硫杂蒽酮衍生物、二苯甲酮及二苯甲酮衍生物中的至少一种。
再者，本发明另一实施例提供一种光刻胶组合物，其中所述光刻胶组合物包含：4至10重量份的树脂基体；5至8重量份的着色剂；大于0且小于 或等于5重量份的自由基聚合单体；大于0且小于或等于0.2重量份的自由基光引发剂；大于0且小于或等于0.002重量份的阳离子光引发剂，其中所述阳离子光引发剂的最大吸收波长在介于280至400纳米之间；及70至80重量份的溶剂。
在本发明的一实施例中，所述阳离子光引发剂选自于二芳基碘鎓盐及其衍生物所组成的一族群。
在本发明的一实施例中，所述二芳基碘鎓盐的衍生物是由下列所组成的一族群所选出：
Figure PCTCN2018106598-appb-000004
及
Figure PCTCN2018106598-appb-000005
其中：
R 1是C nH 2n+1、OC nH 2n+1、C(CH 3) 3或NO 2，其中8<n<20；及
X －是BF 4 －、PF 6 －、SbF 6 －或AsF 6 －。
在本发明的一实施例中，所述树脂基体中包含有丙烯酸树脂及其衍生物中的至少一种。
在本发明的一实施例中，所述丙烯酸树脂的衍生物包含环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂及聚醚丙烯酸树脂中的至少一种。
在本发明的一实施例中，所述着色剂包含偶氮类、喹吖啶酮类、苝系类、钛菁类、蒽醌类、蒽醌类衍生物、吡喏并吡喏二酮类、吡喏并吡喏二酮类衍生物、三芳甲烷类以及三芳甲烷类衍生物中的至少一种。
在本发明的一实施例中，所述自由基聚合单体包含丙烯酸烷基酯、丙烯酸羟基酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、二醇类二丙烯酸酯、烷氧基化丙烯酸酯、乙烯基醚类丙烯酸酯、甲基丙烯酸磷酸酯、含有杂环或苯环的丙烯酸酯以及含有活性胺的丙烯酸酯中的至少一种。
在本发明的一实施例中，所述自由基光引发剂包含硫杂蒽酮、硫杂蒽酮衍生物、二苯甲酮及二苯甲酮衍生物中的至少一种。
在本发明的一实施例中，所述光刻胶组合物还包括为0.1至0.2重量份的添加剂。
为解决上述技术问题，本发明采用的又一个技术方案是：提供一种彩色滤光片，其中所述彩色滤光片涂布有上述任一种的光刻胶组合物。
与现有技术相比较，本发明的光刻胶组合物及彩色滤光片，不受活性氧原子的影响，进而提升光刻胶组合物与基板之间的附着力，并且可适用于高色域或者高色浓度的彩色光刻胶组合物。
具体实施方式
以下各实施例的说明用以例示本发明可用以实施的特定实施例。
本发明实施例提供一种光刻胶组合物，所述光刻胶组合物包括：4至10重量份的树脂基体；5至8重量份的着色剂(亦可称为颜料或染料)；大于0且小于或等于5重量份的自由基聚合单体；大于0且小于或等于0.2重量份的自由基光引发剂；大于0且小于或等于0.002重量份的阳离子光引发剂，其中所述阳离子光引发剂的最大吸收波长在介于280至400纳米之间；及70至80重量份的溶剂。
在一实施例中，所述树脂基体中包含有丙烯酸树脂及其衍生物中的至少一种。在一范例中，所述丙烯酸树脂的衍生物包含环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂及聚醚丙烯酸树脂中的至少一种。
在一实施例中，所述着色剂包含偶氮类、喹吖啶酮类、苝系类、钛菁类、蒽醌类、蒽醌类衍生物、吡喏并吡喏二酮类(DPP类)、吡喏并吡喏二酮类衍生物、三芳甲烷类以及三芳甲烷类衍生物中的至少一种。在一范例中，所述偶氮类颜料对应的索引号包含R144、R37、R38、R41、R111、Y12、Y16或Y17。在另一范例中，所述喹吖啶酮类对应的索引号包含Y138、R209、V19、PR122或PR202。在又一范例中，所述苝系类对应的索引号包含R178、R179、R190、R244、R123、R149、V29。在再一范例中，所述钛菁类对应的索引号包含G58、G59、G63、G7、G36、B15、B15:1、B15:3、B15:4、B15:6或B16；所述蒽醌类对应的索引号包含R177、R83、R168、R216、R226、B21、B22、B60、B64、B65、Y23或Y147；所述吡喏并吡喏二酮类对应的索引号包含R254、R255、R264或R272；所述三芳甲烷类对应的索引号包含B18、B19、B56、B61、B62、V3、V27、V39、R169、R81:1或R81:2。
在一实施例中，所述自由基聚合单体包含丙烯酸烷基酯、丙烯酸羟基酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、二醇类二丙烯酸酯、烷氧基化丙烯酸酯、乙烯基醚类丙烯酸酯、甲基丙烯酸磷酸酯、含有杂环或苯环的丙烯酸酯以及含有活性胺的丙烯酸酯中的至少一种。
在一实施例中，所述阳离子光引发剂选自于二芳基碘鎓盐及其衍生物所组成的一族群。这边要提到的是，所述二芳基碘鎓盐及其衍生物在通过光分解反应后，不仅可引发阳离子聚合，也可引发自由基聚合，故具有较高的光引发效率。
在一范例中，所述二芳基碘鎓盐的结构式如下式(1)所述。
Figure PCTCN2018106598-appb-000006
在另一范例中，所述二芳基碘鎓盐的衍生物是由下列所组成的一族群所选出，如式(2)至式(4)所示：
Figure PCTCN2018106598-appb-000007
及
Figure PCTCN2018106598-appb-000008
其中：
R 1是C nH 2n+1、OC nH 2n+1、C(CH 3) 3或NO 2，其中8<n<20；及
X －是BF 4 －、PF 6 －、SbF 6 －或AsF 6 －。
这边要提到的是，所述二芳基碘鎓盐的衍生物例如是基于提高最大吸收波长的目的，而对所述二芳基碘鎓盐所进行的改质产物。一般而言，所述二芳基碘鎓盐(式(1))虽然最大吸光波大致上是280纳米，但是光吸收率不高。因此，通过改质的方式(例如连接光能吸收率较高的芳酮基团至所述二芳基碘鎓盐上)可使所述二芳基碘鎓盐的衍生物(式(2)至式(4))的最大吸光波长高于所述二芳基碘鎓盐。在一实施例中，如式(2)的所述二芳基碘鎓盐的衍生物的最大吸光波长大致上是250-300纳米。在另一实施例中，如式(3)的所述二芳 基碘鎓盐的衍生物的最大吸光波长大致上是335纳米。在又一实施例中，如式(4)的所述二芳基碘鎓盐的衍生物的最大吸光波长大致上是296或336纳米。
另外要提到的是，当R 1是C nH 2n+1或OC nH 2n+1，为了提高所述阳离子光引发剂在光刻胶组合物的体系中的溶解性，并且降低所述阳离子光引发剂的毒性，n值较佳是位在8与20之间。在一具体范例中，n值例如是9、10、11、12、13、14、15、16、17、18或19。
在一实施例中，所述自由基光引发剂包含硫杂蒽酮、硫杂蒽酮衍生物、二苯甲酮及二苯甲酮衍生物中的至少一种。在一实施例中，所述自由基引发剂可用于拓宽所述阳离子光引发剂(例如二芳基碘鎓盐或其衍生物)的光吸收波长范围(例如提高最大光吸收波长)。所述自由基引发剂吸收光能后，可将电子转移给所述阳离子光引发剂(例如二芳基碘鎓盐或其衍生物)，从而产生超强酸。所述超强酸可引发阳离子聚合反应和自由基聚合反应。
在一具体范例中，所述二芳基碘鎓盐如式(5)至式(7)的结构，在搭配与自由基引发剂硫杂蒽酮、二苯甲酮等类别物质后可产生超强酸，同时引发阳离子聚合反应和自由基聚合反应。下式中的SbF 6 －亦可替换为BF 4 －、PF 6 －或AsF 6 -。
Figure PCTCN2018106598-appb-000009
其中，8<n<20。
另外，式(5)至式(7)的结构含有支链为C原子数量大于8的烷烃链状结构，该结构可以提高该引发剂使用时在体系中的溶解性，降低毒性。
在一实施例中，所述光刻胶组合物还包括为0.1至0.2重量份的添加剂。在一范例中，所述添加剂包含润湿分散剂、流平剂及阻聚剂中的至少一种。
为解决上述技术问题，本发明采用的另一个技术方案是：提供一种彩色滤光片，其中所述彩色滤光片涂布有上述任一种的光刻胶组合物。具体的，所述彩色滤光片包括：基板；设置在所述基板上的黑矩阵；和设置在所述黑矩阵上的彩色滤光层，所述彩色滤光层由本发明实施方式中提供的光刻胶组合物形成。进一步的，在所述彩色滤光片各个膜层上涂布所述光刻胶组合物，所述光刻胶组合物不受活性氧原子的影响，进而提升光刻胶组合物与基板之间的附着力，可提升所述彩色滤光片的良率。
这边要提到的是，本发明的光刻胶组合物及使用其的彩色滤光片涉及于阳离子光固化体系，并且具有以下优点。
1.添加二芳基碘鎓盐作为阳离子光引发剂的方法可适用于当前高色浓度光刻胶材料，由于阳离子光引发剂的添加量少(例如约为大于0且小于或等于0.002重量百分比)，且不需额外添加阳离子单体，因此不会产生其他材料成分的比例受到限制的问题。
2.本发明实施例的光刻胶组合物是在原有的配方基础上，把自由基光引发剂的一部分替换为阳离子光引发剂，故不影响原有体系光固化特性，且可与原自由基固化体系(例如丙烯酸类树脂类)具有较好的兼容性。此外，阳离子光引发剂除了可引发阳离子聚合，也同时可引发自由基聚合，引发效率较高。
3.阳离子光引发剂不受基板表面活性氧影响，不会发生氧阻聚及引发剂失活，固化收缩率小，有利于增加光刻胶组合物对基材的附着力。
4.这种阳离子光固化体系有很好的深层固化性，故可降低或避免光刻胶剥落的风险。
5.涉及阳离子引发体系的光刻胶组合物具有较小的体积收缩率(相对于自由基引发体系)，且在光固化反应后具有后固化(post curing)的特点，进一步加强光刻胶组合物的硬化性。
本发明已由上述相关实施例加以描述，然而上述实施例仅为实施本发明的范例。必需指出的是，已公开的实施例并未限制本发明的范围。相反地，包含于权利要求书的精神及范围的修改及均等设置均包括于本发明的范围内。

Claims (17)

  1. 一种光刻胶组合物，其包含：
    4至10重量份的树脂基体；
    5至8重量份的着色剂；
    大于0且小于或等于5重量份的自由基聚合单体；
    大于0且小于或等于0.2重量份的自由基光引发剂；
    大于0且小于或等于0.002重量份的阳离子光引发剂，其中所述阳离子光引发剂的最大吸收波长在介于280至400纳米之间，以及所述阳离子光引发剂选自于二芳基碘鎓盐及其衍生物所组成的一族群；
    70至80重量份的溶剂；及
    0.1至0.2重量份的添加剂。
  2. 如权利要求1所述的光刻胶组合物，其中所述二芳基碘鎓盐的衍生物是由下列所组成的一族群所选出：
    Figure PCTCN2018106598-appb-100001
    Figure PCTCN2018106598-appb-100002
    及
    Figure PCTCN2018106598-appb-100003
    其中：
    R 1是C nH 2n+1、OC nH 2n+1、C(CH 3) 3或NO 2，其中8<n<20；及
    X －是BF 4 －、PF 6 －、SbF 6 －或AsF 6 －。
  3. 如权利要求1所述的光刻胶组合物，其中所述树脂基体中包含有丙烯酸树脂及其衍生物中的至少一种。
  4. 如权利要求3所述的光刻胶组合物，其中所述丙烯酸树脂的衍生物包含环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂及聚醚丙烯酸树脂中的至少一种。
  5. 如权利要求1所述的光刻胶组合物，其中所述着色剂包含偶氮类、喹吖啶酮类、苝系类、钛菁类、蒽醌类、蒽醌类衍生物、吡喏并吡喏二酮类、吡喏并吡喏二酮类衍生物、三芳甲烷类以及三芳甲烷类衍生物中的至少一种。
  6. 如权利要求1所述的光刻胶组合物，其中所述自由基聚合单体包含丙烯酸烷基酯、丙烯酸羟基酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、二醇类二丙烯酸酯、烷氧基化丙烯酸酯、乙烯基醚类丙烯酸酯、甲基丙烯酸磷酸酯、含有杂环或苯环的丙烯酸酯以及含有活性胺的丙烯酸酯中的至少一种。
  7. 如权利要求1所述的光刻胶组合物，其中所述自由基光引发剂包含硫杂蒽酮、硫杂蒽酮衍生物、二苯甲酮及二苯甲酮衍生物中的至少一种。
  8. 一种光刻胶组合物，其包含：
    4至10重量份的树脂基体；
    5至8重量份的着色剂；
    大于0且小于或等于5重量份的自由基聚合单体；
    大于0且小于或等于0.2重量份的自由基光引发剂；
    大于0且小于或等于0.002重量份的阳离子光引发剂，其中所述阳离子光引发剂的最大吸收波长在介于280至400纳米之间；及
    70至80重量份的溶剂。
  9. 如权利要求8所述的光刻胶组合物，其中所述阳离子光引发剂选自于二芳基碘鎓盐及其衍生物所组成的一族群。
  10. 如权利要求9所述的光刻胶组合物，其中所述二芳基碘鎓盐的衍生物是由下列所组成的一族群所选出：
    Figure PCTCN2018106598-appb-100004
    Figure PCTCN2018106598-appb-100005
    及
    Figure PCTCN2018106598-appb-100006
    其中：
    R 1是C nH 2n+1、OC nH 2n+1、C(CH 3) 3或NO 2，其中8<n<20；及
    X －是BF 4 －、PF 6 －、SbF 6 －或AsF 6 －。
  11. 如权利要求8所述的光刻胶组合物，其中所述树脂基体中包含有丙烯酸树脂及其衍生物中的至少一种。
  12. 如权利要求11所述的光刻胶组合物，其中所述丙烯酸树脂的衍生物包含环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂及聚醚丙烯酸树脂中的至少一种。
  13. 如权利要求8所述的光刻胶组合物，其中所述着色剂包含偶氮类、喹吖啶酮类、苝系类、钛菁类、蒽醌类、蒽醌类衍生物、吡喏并吡喏二酮类、吡喏并吡喏二酮类衍生物、三芳甲烷类以及三芳甲烷类衍生物中的至少一 种。
  14. 如权利要求8所述的光刻胶组合物，其中所述自由基聚合单体包含丙烯酸烷基酯、丙烯酸羟基酯、乙烯基活性稀释剂、乙二醇类二丙烯酸酯、丙二醇类二丙烯酸酯、二醇类二丙烯酸酯、烷氧基化丙烯酸酯、乙烯基醚类丙烯酸酯、甲基丙烯酸磷酸酯、含有杂环或苯环的丙烯酸酯以及含有活性胺的丙烯酸酯中的至少一种。
  15. 如权利要求8所述的光刻胶组合物，其中所述自由基光引发剂包含硫杂蒽酮、硫杂蒽酮衍生物、二苯甲酮及二苯甲酮衍生物中的至少一种。
  16. 如权利要求8所述的光刻胶组合物，其中所述光刻胶组合物还包括为0.1至0.2重量份的添加剂。
  17. 一种彩色滤光片，涂布有如权利要求8所述的光刻胶组合物。
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