TW202307139A - Photosensitive colored resin composition, cured product, color filter and display device - Google Patents
Photosensitive colored resin composition, cured product, color filter and display device Download PDFInfo
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- 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
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- 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
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- 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
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Abstract
Description
本發明係關於一種感光性著色樹脂組合物、硬化物、彩色濾光片、及顯示裝置。The present invention relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device.
近年來,隨著個人電腦之發展、尤其是攜帶用個人電腦之發展,液晶顯示器之需求有所增加。行動顯示器(行動電話、智慧型手機、平板PC)之普及率亦提高,液晶顯示器之市場處於日益擴大之情況。如藉由自發光而視認性較高之有機EL(Electroluminescence,電致發光)顯示器之有機發光顯示裝置亦作為下一代圖像顯示裝置而受到關注。 該等液晶顯示裝置或有機發光顯示裝置使用彩色濾光片。例如液晶顯示裝置之彩色圖像之形成係通過彩色濾光片之光直接被著色為構成彩色濾光片之各像素之顏色,將該等顏色之光合成而形成彩色圖像。作為此時之光源,除了先前之冷陰極管以外,存在利用白色發光之有機發光元件或白色發光之無機發光元件之情形。於有機發光顯示裝置中,為了進行顏色調整等,而使用彩色濾光片。In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, and tablet PCs) is also increasing, and the market for liquid crystal displays is expanding day by day. An organic light-emitting display device such as an organic EL (Electroluminescence, electroluminescence) display with high visibility due to self-luminescence is also attracting attention as a next-generation image display device. These liquid crystal display devices or organic light emitting display devices use color filters. For example, the formation of a color image of a liquid crystal display device is that the light passing through the color filter is directly colored into the color of each pixel constituting the color filter, and the light of these colors is synthesized to form a color image. As a light source at this time, besides the conventional cold-cathode tube, there are cases where an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is used. In organic light emitting display devices, color filters are used for color adjustment and the like.
此處,彩色濾光片通常具有:基板;著色層,形成於基板上,包含紅、綠、藍之三原色之著色圖案;及遮光部,以劃分各著色圖案之方式形成於基板上。 作為彩色濾光片中之著色層之形成方法,例如,將於藉由分散劑等將色材分散而成之色材分散液中添加黏合劑樹脂、光聚合性化合物及光起始劑而成之著色樹脂組合物塗佈於玻璃基板並加以乾燥後,使用光罩進行曝光並進行顯影,藉此形成著色圖案,進行加熱,藉此將圖案固定,形成著色層。針對各顏色分別重複該等步驟,而形成彩色濾光片。 Here, a color filter generally includes: a substrate; a colored layer formed on the substrate and including colored patterns of three primary colors of red, green, and blue; and a light shielding portion formed on the substrate to divide each colored pattern. As a method of forming a colored layer in a color filter, for example, a binder resin, a photopolymerizable compound, and a photoinitiator are added to a color material dispersion obtained by dispersing a color material with a dispersant or the like. The colored resin composition is coated on a glass substrate and dried, then exposed and developed using a photomask to form a colored pattern, and then heated to fix the pattern to form a colored layer. These steps are repeated for each color to form a color filter.
近年來,對彩色濾光片之高亮度化等要求越來越高,藉由使用顏料之彩色濾光片難以達成現在更高亮度化之要求。 因此,近年來,正研究使用與顏料相比通常透過率較高之染料、或利用沈澱劑使染料成為不溶性而成之色澱色材作為彩色濾光片用之色材。 然而,染料或色澱色材與目前作為彩色濾光片用之色材所使用之顏料相比,存在如下問題:耐熱性較差,於彩色濾光片製造步驟中之高溫加熱時,著色層容易退色。 In recent years, the requirements for higher brightness of color filters have become higher and higher, and it is difficult to achieve the current higher brightness requirements by color filters using pigments. Therefore, in recent years, the use of dyes with higher transmittance than pigments or lake color materials made of dyes insoluble by precipitating agents has been studied as color materials for color filters. However, compared with pigments currently used as color materials for color filters, dyes or lake color materials have the following problems: heat resistance is poor, and the colored layer is easily damaged when heated at a high temperature in the color filter manufacturing process. fade.
與此相對,於專利文獻1中,作為使用色澱顏料,並且抑制彩色濾光片製造步驟中之高溫加熱導致之著色層之退色,能夠形成高亮度之著色層之彩色濾光片用著色樹脂組合物,而揭示有如下一種彩色濾光片用著色樹脂組合物,其含有色澱顏料、分散劑、受阻酚系抗氧化劑、黏合劑成分、及溶劑,上述分散劑為氮部位之至少一部分與酸性有機磷化合物形成鹽而成之特定之聚合物。On the other hand, in
另一方面,作為含有紫外線吸收劑之感光性著色組合物,專利文獻2中揭示有一種著色樹脂組合物,其係含有(A)染料、(B)溶劑、及(C)黏合劑樹脂之著色樹脂組合物,其特徵在於進而含有(D)抗氧化劑及(E)紫外線吸收劑。專利文獻2之課題在於提供一種能夠維持提高所獲得之像素之亮度及耐熱性,並且進而形成所需直徑之接觸孔。 又,專利文獻3中揭示有一種感光性著色組合物,其特徵在於:包含著色劑(A)、樹脂(B)、光聚合性單體(C)、含有醯基氧化膦系有機化合物或肟酯系有機化合物之光聚合起始劑(D)、及作為選自由苯并三唑系有機化合物、三𠯤系有機化合物、及二苯甲酮系有機化合物所組成之群中之至少1種之紫外線吸收劑(E),且樹脂(B)包含感光性樹脂(B-1),該感光性樹脂(B-1)係使下述(b1)、(b2)及(b3)共聚而獲得共聚物(b6),使所獲得之共聚物(b6)與不飽和一元酸(b4)進行反應獲得共聚物(b7),進而使所獲得之共聚物(b7)與多元酸酐(b5)進行反應而獲得者: (b1):1分子中具有脂環式骨架及乙烯性不飽和鍵之化合物; (b2):1分子中具有環氧基及乙烯性不飽和鍵之化合物; (b3):除(a1)及(a2)以外之具有乙烯性不飽和鍵之化合物。 於專利文獻3中,其課題在於獲得一種具有能夠應對高畫質化、低耗電化之高解像性之感光性著色組合物、尤其是即便為如COA(Color Filter on Array)方式之厚膜亦為高解像度、不發生圖案剝離之密接性優異之感光性著色組合物。 先前技術文獻 專利文獻On the other hand, as a photosensitive coloring composition containing an ultraviolet absorber,
專利文獻1:日本專利特開2014-153569號公報 專利文獻2:日本專利特開2015-98537號公報 專利文獻3:日本專利第5664299號公報 Patent Document 1: Japanese Patent Laid-Open No. 2014-153569 Patent Document 2: Japanese Patent Laid-Open No. 2015-98537 Patent Document 3: Japanese Patent No. 5664299
[發明所欲解決之問題][Problem to be solved by the invention]
伴隨顯示器之4K/8K等高精細化,像素尺寸變小,對應於像素之開口部比率(開口率)之降低,而要求更高亮度之抗蝕劑,並且要求能夠形成線寬較細之圖案之感光性著色樹脂組合物。 然而,於如專利文獻2般將染料溶解而使用之情形時,尤其是耐熱性較差,像素之亮度提高不足,於如專利文獻3般使用顏料之技術中,像素之亮度提高不足。 作為對於像素之高亮度化有效之色材,可例舉三芳基甲烷系染料之色澱色材。然而,三芳基甲烷系染料之色澱色材與先前所使用之顏料(例如C.I.顏料藍15:6、C.I.顏料紫23)相比,UV波長區域之透過率較高,因此若與先前同樣地調配光起始劑,則圖案線寬容易變粗。若為了使圖案線寬符合規定值,而減少光起始劑量、或如專利文獻1般添加抗氧化劑、或增加抗氧化劑之添加量,則圖案部分之光硬化性不足,顯影前至顯影後之膜厚變化增大,顯影殘膜率降低,難以同時實現較細之線寬設計與較高之顯影殘膜率。 雖然專利文獻1中記載有三芳基甲烷系染料之色澱色材,但關於同時實現較細之線寬設計與較高之顯影殘膜率之課題並無提示。專利文獻2中記載有包含三芳基甲烷系染料之感光性著色樹脂組合物。然而,由於染料係以分子等級分散於感光性著色樹脂組合物中,故而容易抑制光硬化性成分之硬化性,若與顏料同樣地調配光起始劑,則光硬化性不足,線寬容易變得比設計更細,顯影殘膜率容易降低。因此,於含有染料之感光性著色樹脂組合物中,為了設為所需之較細之線寬,需要增多光起始劑、或使用更高感度之光起始劑,因此顯影殘膜率會自然地提高。因此,於含有染料之感光性著色樹脂組合物中,本來就不存在難以同時實現較細之線寬設計與較高之顯影殘膜率之課題。又,專利文獻3係使用顏料,因此本來就不存在難以同時實現較細之線寬設計與較高之顯影殘膜率之課題。 如上所述,於使用三芳基甲烷系染料之色澱色材之情形時,不同於使用顏料之情形或使用染料之情形,存在難以同時實現較細之線寬設計與較高之顯影殘膜率之課題。With the high-definition of 4K/8K displays, the size of the pixel becomes smaller, corresponding to the reduction of the aperture ratio (aperture ratio) of the pixel, a resist with higher brightness is required, and it is required to be able to form a pattern with a thinner line width A photosensitive colored resin composition. However, when the dye is dissolved and used as in
本發明係鑒於上述實際情況而完成,其目的在於提供一種感光性著色樹脂組合物,該感光性著色樹脂組合物含有三芳基甲烷系染料之色澱色材,能夠形成提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層。又,本發明之目的在於提供一種使用該感光性著色樹脂組合物所形成之彩色濾光片及顯示裝置。 [解決問題之技術手段] The present invention is made in view of the above-mentioned actual situation, and its object is to provide a kind of photosensitive coloring resin composition, this photosensitive coloring resin composition contains the color lake color material of triarylmethane series dye, can form and improve brightness and by finer The line width of the coloring layer suppresses the change in film thickness before and after development. Moreover, the object of this invention is to provide the color filter and display apparatus formed using this photosensitive colored resin composition. [Technical means to solve the problem]
本發明之感光性著色樹脂組合物含有色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及溶劑, 上述色材含有三芳基甲烷系染料之色澱色材。 The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, The above-mentioned color material contains a lake color material of a triarylmethane dye.
本發明之彩色濾光片係至少具備基板、及設置於該基板上之著色層之彩色濾光片,該著色層之至少一者為上述本發明之感光性著色樹脂組合物之硬化物。The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, at least one of which is a cured product of the photosensitive colored resin composition of the present invention.
本發明之顯示裝置具有上述本發明之彩色濾光片。 [發明之效果] The display device of the present invention has the above-mentioned color filter of the present invention. [Effect of Invention]
根據本發明,能夠提供一種含有三芳基甲烷系染料之色澱色材且能夠形成提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層的感光性著色樹脂組合物。又,根據本發明,能夠提供一種使用該感光性著色樹脂組合物所形成之彩色濾光片及顯示裝置。According to the present invention, it is possible to provide a photosensitive colored resin composition that contains a triarylmethane-based dye lake coloring material and can form a colored layer that improves brightness and suppresses changes in film thickness before and after development due to thinner line widths. Also, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided.
以下,依序對本發明之感光性著色樹脂組合物、硬化物、彩色濾光片、及顯示裝置進行詳細說明。 再者,於本發明中,光包括可見光及非可見光區域之波長之電磁波,進而包括放射線,放射線例如包括微波、電子束。具體而言,指波長5 μm以下之電磁波、及電子束。 於本發明中,(甲基)丙烯醯基表示丙烯醯基及甲基丙烯醯基之各者,(甲基)丙烯酸基表示丙烯酸基及甲基丙烯酸基之各者,(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯之各者。 又,於本說明書中,表示數值範圍之「~」係以包括其前後所記載之數值作為下限值及上限值之含義使用。 Hereinafter, the photosensitive colored resin composition, cured product, color filter, and display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves of wavelengths in the visible light and non-visible light regions, and further includes radiation. For example, radiation includes microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, (meth)acryl means each of acryl and methacryl, (meth)acryl means each of acryl and methacryl, (meth)acrylate Represents each of acrylate and methacrylate. In addition, in this specification, "-" which shows a numerical range is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.
I.感光性著色樹脂組合物 本發明之感光性著色樹脂組合物含有色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及溶劑, 上述色材含有三芳基甲烷系染料之色澱色材。 I. Photosensitive colored resin composition The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, The above-mentioned color material contains a lake color material of a triarylmethane dye.
本發明之感光性著色樹脂組合物含有色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及溶劑,且上述色材為三芳基甲烷系染料之色澱色材,因此能夠形成提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層。作為發揮此種效果之作用尚未明瞭,推定如以下所述。The photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the above-mentioned coloring material is a triarylmethane-based dye lake coloring material, Therefore, it is possible to form a colored layer that improves luminance and suppresses changes in film thickness before and after development with thinner line widths. The function of exerting such an effect is not clear, but it is estimated as follows.
如上文所述,顏料之紫外線之透過率較低,因此於含有顏料之感光性著色樹脂組合物中,光硬化性成分相對難以硬化。又,染料容易抑制光硬化性成分之硬化性,因此於含有染料之感光性著色樹脂組合物中,光硬化性成分亦相對難以硬化。與此相對,三芳基甲烷系染料之色澱色材由於紫外線之透過率較高,且不存在抑制光硬化性成分之硬化性之情況,故而光硬化後不溶於顯影液之效果高於顏料或染料,因此圖案線寬容易變粗。於含有三芳基甲烷系染料之色澱色材之感光著色樹脂組合物中,為了將圖案線寬設為規定之較細之線寬,需要有效地抑制光硬化反應。 作為色材,使用透過率較高之三芳基甲烷系染料之色澱色材,認為若為了使圖案線寬符合規定值,而減少光起始劑量,則不論膜厚方向如何均會減少光反應之自由基生成,因此圖案部分之光硬化性不足,顯影前至顯影後之膜厚變化增大,顯影殘膜率降低。又,使用三芳基甲烷系染料之色澱色材,認為若為了使圖案線寬符合規定值而添加抗氧化劑或增加其量,則不論膜厚方向如何均會使藉由光起始劑之光反應所生成之自由基失活,因此圖案部分之光硬化性不足,顯影前至顯影後之膜厚變化增大,顯影殘膜率降低。 與此相對,於本發明中,於三芳基甲烷系染料之色澱色材中組合紫外線吸收劑。認為紫外線吸收劑於膜表面不會使紫外線衰減,因此顯影殘膜不會降低,伴隨到達膜深部而使紫外線衰減,減少自由基自起始劑之生成,如此根據膜之深度發揮作用,因此能夠抑制顯影後殘膜之膜厚降低,並且減小線寬。 進而,由於色材包含三芳基甲烷系染料之色澱色材,故而作為本發明之感光性著色樹脂組合物之硬化物之著色層的透過率較高,且紫外線照射或後烘烤等製造時之步驟引起之色度變化受到抑制。因此,本發明之感光性著色樹脂組合物能夠提供最終獲得之著色層之亮度。 As mentioned above, the ultraviolet transmittance of the pigment is low, so in the photosensitive colored resin composition containing the pigment, it is relatively difficult to harden the photocurable component. Moreover, since a dye tends to suppress the curability of a photocurable component, in the photosensitive colored resin composition containing a dye, a photocurable component is relatively difficult to harden. In contrast, the color lake material of triarylmethane dyes has a higher transmittance of ultraviolet rays and does not inhibit the hardening of photocurable components, so the effect of insolubility in developing solutions after photocuring is higher than that of pigments or dye, so the pattern line width tends to become thicker. In the photosensitive coloring resin composition containing the lake material of a triarylmethane dye, it is necessary to effectively suppress the photocuring reaction in order to make the pattern line width a predetermined thinner line width. As a coloring material, a triarylmethane-based dye lake coloring material with high transmittance is used. It is believed that if the initial dose of light is reduced in order to make the pattern line width meet the specified value, the photoreaction will be reduced regardless of the film thickness direction. Free radicals are generated, so the photocurability of the pattern part is insufficient, the film thickness change from before to after development increases, and the residual film rate after development decreases. In addition, for the lake color material using triarylmethane dyes, it is considered that if an antioxidant is added or its amount is increased in order to make the pattern line width meet the specified value, the light passing through the photoinitiator will be blocked regardless of the film thickness direction. The free radicals generated by the reaction are deactivated, so the photocurability of the pattern part is insufficient, the film thickness change from before to after development is increased, and the residual film rate after development is reduced. On the other hand, in the present invention, an ultraviolet absorber is combined with the lake material of a triarylmethane dye. It is considered that the ultraviolet absorber will not attenuate the ultraviolet rays on the surface of the film, so the residual film will not be reduced, and it will attenuate the ultraviolet rays as it reaches the deep part of the film, reducing the generation of free radicals from the initiator. This works according to the depth of the film, so it can Suppresses reduction in film thickness of residual film after development and reduces line width. Furthermore, since the coloring material includes a lake coloring material of a triarylmethane dye, the transmittance of the coloring layer as a hardened product of the photosensitive colored resin composition of the present invention is high, and it is difficult to produce a coloring layer by ultraviolet irradiation or post-baking. Chromaticity changes caused by the steps are suppressed. Therefore, the photosensitive colored resin composition of the present invention can provide the brightness of the finally obtained colored layer.
本發明之感光性著色樹脂組合物至少含有色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及溶劑,於不損及本發明之效果之範圍內,可進一步含有其他成分。例如,本發明之感光性著色樹脂組合物為了提高色材分散性,可進一步含有分散劑。 以下,對於此種本發明之感光性著色樹脂組合物之各成分,首先自紫外線吸收劑起,依序進行詳細說明。 The photosensitive colored resin composition of the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and may further contain other ingredients. For example, the photosensitive colored resin composition of the present invention may further contain a dispersant in order to improve the dispersibility of the color material. Hereinafter, each component of the photosensitive colored resin composition of the present invention will be described in detail sequentially from the ultraviolet absorber first.
[紫外線吸收劑] 本發明中之紫外線吸收劑係指於400 nm以下具有吸收極大波長、於波長超過420 nm之可見光下不具有吸收之化合物。本發明所使用之紫外線吸收劑可為於波長超過400 nm之可見光下不具有吸收波長之化合物。 [ultraviolet absorber] The ultraviolet absorber in the present invention refers to a compound that has a maximum absorption wavelength below 400 nm and has no absorption under visible light with a wavelength exceeding 420 nm. The ultraviolet absorber used in the present invention may be a compound having no absorption wavelength under visible light with a wavelength exceeding 400 nm.
本發明所使用之紫外線吸收劑之結構並無特別限定。作為紫外線吸收劑,例如可例舉:苯并三唑系紫外線吸收劑、三𠯤系紫外線吸收劑、二苯甲酮系紫外線吸收劑、苯甲酸酯系紫外線吸收劑、苯甲酸系紫外線吸收劑、鄰胺苯甲酸系紫外線吸收劑、水楊酸系紫外線吸收劑、桂皮酸系紫外線吸收劑等。The structure of the ultraviolet absorber used in the present invention is not particularly limited. Examples of the ultraviolet absorber include: benzotriazole-based ultraviolet absorbers, trisulfone-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and benzoic acid-based ultraviolet absorbers. , Anthranilic acid-based UV absorbers, salicylic acid-based UV absorbers, cinnamic acid-based UV absorbers, etc.
例如,作為苯并三唑系紫外線吸收劑,可例舉選自由下述通式(A)所表示之苯并三唑系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑。For example, the benzotriazole-based ultraviolet absorber may, for example, be at least one ultraviolet absorber selected from the group consisting of benzotriazole-based ultraviolet absorbers represented by the following general formula (A).
[化1] (於通式(A)中,X 1、X 2、及X 3分別獨立地表示氫原子、羥基、-OR a、或可具有取代基之碳原子數1~15之烴基,R a表示可具有取代基之碳原子數1~15之烴基,X 1、X 2、及X 3之至少一者表示羥基、-OR a、或可具有取代基之碳原子數1~15之烴基。X 4表示氫原子或鹵素原子) [chemical 1] (In the general formula (A), X 1 , X 2 , and X 3 each independently represent a hydrogen atom, a hydroxyl group, -OR a , or a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and R a represents an optional A hydrocarbon group having 1 to 15 carbon atoms having a substituent, at least one of X 1 , X 2 , and X 3 represents hydroxyl, -OR a , or a hydrocarbon group having 1 to 15 carbon atoms that may have a substituent. X 4 represents a hydrogen atom or a halogen atom)
於通式(A)中,X 1、X 2、及X 3、以及R a中之上述碳原子數1~15之烴基可例舉直鏈或支鏈狀之脂肪族烴基、芳香族烴基,可例舉:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、十二烷基、苯基、萘基、聯苯基等。上述烴基之碳原子數可為1~12,亦可為1~8。上述烴基可為脂肪族烴基,亦可為直鏈或支鏈之烷基,亦可為甲基、第三丁基、第三戊基、正辛基、第三辛基(1,1,3,3-四甲基丁基)、2-乙基己基。 作為取代基,例如可例舉:鹵素原子、羥基、氰基、或包含羰基、酯基、醚基、醯胺基、醯亞胺基等之基,可為醯基、醯氧基、烷氧基、芳氧基、縮水甘油基等。進而作為芳香族烴基之取代基,亦可為烷基。 作為具有取代基之烴基,例如可為-C 2H 3(OH)-CH 2-O-C 8H 17、-C 2H 3(OH)-CH 2-O-C 12H 25、-CH(CH 3)-CO 2-C 8H 17、甲基丙烯醯氧基乙基等,又,亦可為4-甲基苯基、3-氯苯基、4-苄氧基苯基、4-氰基苯基、4-苯氧基苯基、4-縮水甘油氧基苯基、4-異氰尿酸基苯基等。上述-C 8H 17、-C 12H 25等分別可為直鏈或支鏈。 於通式(A)中,作為上述鹵素原子,可例舉:氯原子、氟原子、溴原子等。 In the general formula (A), the above-mentioned hydrocarbon groups having 1 to 15 carbon atoms in X 1 , X 2 , and X 3 , and R a can be straight-chain or branched aliphatic hydrocarbon groups and aromatic hydrocarbon groups, Examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, phenyl, naphthyl, biphenyl and the like. The number of carbon atoms in the above-mentioned hydrocarbon group may be 1-12, or may be 1-8. The above-mentioned hydrocarbon groups can be aliphatic hydrocarbon groups, also can be linear or branched chain alkyl groups, can also be methyl, tertiary butyl, tertiary pentyl, n-octyl, tertiary octyl (1,1,3 , 3-tetramethylbutyl), 2-ethylhexyl. As a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, or a group including a carbonyl group, an ester group, an ether group, an amido group, an imide group, etc., may be mentioned, and may be an acyl group, an acyloxy group, or an alkoxy group. group, aryloxy group, glycidyl group, etc. Furthermore, an alkyl group may be used as a substituent of an aromatic hydrocarbon group. Examples of hydrocarbon groups having substituents include -C 2 H 3 (OH)-CH 2 -OC 8 H 17 , -C 2 H 3 (OH)-CH 2 -OC 12 H 25 , -CH(CH 3 ) -CO 2 -C 8 H 17 , methacryloxyethyl, etc., and 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanobenzene 4-phenoxyphenyl, 4-glycidyloxyphenyl, 4-isocyanuratophenyl, etc. Each of the aforementioned -C 8 H 17 , -C 12 H 25 , etc. may be linear or branched. In the general formula (A), examples of the halogen atom include a chlorine atom, a fluorine atom, and a bromine atom.
作為苯并三唑系紫外線吸收劑,例如可例舉:2-(5-甲基-2-羥基苯基)苯并三唑、2-(2-羥基-5-第三丁基苯基)-2H-苯并三唑、3[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯與3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸2-乙基己酯之混合物、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-2H-苯并三唑、2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并三唑、2-(3,5-二第三戊基-2-羥基苯基)苯并三唑、2-(2'-羥基-5'-第三辛基苯基)苯并三唑、2-(2H-苯并三唑-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚等。Examples of benzotriazole-based ultraviolet absorbers include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 3-[3 -Mixture of tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propanoic acid 2-ethylhexyl ester, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5- Chlorobenzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzo Triazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2- base)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc.
例如,作為三𠯤系紫外線吸收劑,可例舉選自由下述通式(B)所表示之三𠯤系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑。For example, at least one ultraviolet absorber selected from the group consisting of trioxane-based ultraviolet absorbents represented by the following general formula (B) may be mentioned as the trioxane-based ultraviolet absorber.
[化2]
(於通式(B)中,Y
1、Y
2、Y
3、Y
4、Y
5、及Y
6分別獨立地表示氫原子、羥基、-OR
b、或可具有取代基之碳原子數1~15之烴基,R
b表示可具有取代基之碳原子數1~15之烴基,Y
1、Y
2、Y
3、Y
4、Y
5、及Y
6之至少一者表示羥基、-OR
b、或可具有取代基之碳原子數1~15之烴基)
[Chem 2] (In the general formula (B), Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , and Y 6 each independently represent a hydrogen atom, a hydroxyl group, -OR b , or a
Y 1、Y 2、Y 3、Y 4、Y 5、及Y 6、以及R b中之可具有取代基之碳原子數1~15之烴基可與上述X 1、X 2、及X 3、以及R a中之上述可具有取代基之碳原子數1~15之烴基相同。 Y 2、Y 4、及Y 6之至少一者可為羥基,亦可為羥基苯基三𠯤系紫外線吸收劑。 In Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , and Y 6 , and a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent in R b , it can be combined with the above-mentioned X 1 , X 2 , and X 3 , and the above-mentioned hydrocarbon group having 1 to 15 carbon atoms which may have a substituent in R a are the same. At least one of Y 2 , Y 4 , and Y 6 may be a hydroxyl group, or may be a hydroxyphenyl trisulfone-based ultraviolet absorber.
作為三𠯤系紫外線吸收劑,例如可例舉:2-[4,6-二(2,4-二甲苯基)-1,3,5-三𠯤-2-基]-5-辛氧基苯酚、2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤-2-基]-5-[3-(十二烷氧基)-2-羥基丙氧基]苯酚、2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三𠯤等。Examples of trioxane-based ultraviolet absorbers include: 2-[4,6-bis(2,4-xylyl)-1,3,5-trizil-2-yl]-5-octyloxy Phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl]-5-[3-(dodecyloxy)-2 -Hydroxypropoxy]phenol, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-tributoxyphenyl wait.
例如,作為二苯甲酮系紫外線吸收劑,可例舉羥基二苯甲酮系紫外線吸收劑,可例舉選自由下述通式(C)所表示之羥基二苯甲酮系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑。For example, the benzophenone-based ultraviolet absorber may, for example, be a hydroxybenzophenone-based ultraviolet absorber, which may be selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by the following general formula (C). At least one ultraviolet absorber of the group formed.
[化3] (於通式(C)中,Z 1表示羥基、-OR c、或可具有取代基之碳原子數1~15之烴基,Z 2表示氫原子、羥基、-OR c、或可具有取代基之碳原子數1~15之烴基,Z 3表示氫原子或羥基,R c表示可具有取代基之碳原子數1~15之烴基) [Chem 3] (In the general formula (C), Z 1 represents a hydroxyl group, -OR c , or a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent, and Z 2 represents a hydrogen atom, a hydroxyl group, -OR c , or a hydrocarbon group that may have a substituent A hydrocarbon group with 1 to 15 carbon atoms, Z 3 represents a hydrogen atom or a hydroxyl group, R c represents a hydrocarbon group with 1 to 15 carbon atoms that may have a substituent)
於通式(C)中,Z 1、及Z 2、以及R c中之可具有取代基之碳原子數1~15之烴基可與上述X 1、X 2、及X 3、以及R a中之上述可具有取代基之碳原子數1~15之烴基相同。 In the general formula (C), the hydrocarbon groups with 1 to 15 carbon atoms which may have substituents in Z 1 , Z 2 , and R c can be combined with the above-mentioned X 1 , X 2 , and X 3 , and R a The aforementioned hydrocarbon groups having 1 to 15 carbon atoms which may have substituents are the same.
作為二苯甲酮系紫外線吸收劑,例如可例舉:2,4-二羥基二苯甲酮、2-羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-正辛氧基二苯甲酮、2,2-二羥基-4-甲氧基二苯甲酮等。Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- Hydroxy-4-n-octyloxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, etc.
本發明所使用之紫外線吸收劑之重量平均分子量就高效地吸收紫外線之方面而言,通常為80以上,較佳為150以上,進而較佳為300以上,又,通常為2000以下,較佳為1500以下,進而較佳為900以下。又,紫外線吸收劑之聚合物由於紫外線吸收能力較低,故而較佳為不具有重複單元之非聚合物之化合物。The weight average molecular weight of the ultraviolet absorber used in the present invention is usually 80 or more, preferably 150 or more, further preferably 300 or more, and usually 2000 or less, preferably 2000 or less, in terms of efficiently absorbing ultraviolet rays 1500 or less, more preferably 900 or less. In addition, the polymer of the ultraviolet absorber is preferably a non-polymer compound having no repeating unit because the ultraviolet absorbing ability is low.
本發明所使用之紫外線吸收劑較佳為選擇使用於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率為45%以下之紫外線吸收劑。若如上所述,將波長365 nm下之透過率較小之紫外線吸收劑與三芳基甲烷系染料之色澱色材組合使用,則能夠有效地減弱三芳基甲烷色澱色材之吸收較弱且超高壓水銀燈之照射強度最高之紫外線之強度,其結果,就能夠添加充分確保塗膜表面之硬化性之量之起始劑而抑制顯影殘後之膜厚變化,並且有效地減弱塗膜內部之光硬化性,容易以線寬偏移量不會變得過大之方式進行調整之方面而言較佳。The ultraviolet absorber used in the present invention is preferably an ultraviolet absorber with a transmittance of 45% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution. If, as mentioned above, the ultraviolet absorber with a lower transmittance at a wavelength of 365 nm is used in combination with the color lake material of triarylmethane dyes, it can effectively reduce the weak absorption of the triarylmethane color lake material and Ultra-high pressure mercury lamp has the highest irradiation intensity of ultraviolet rays. As a result, it is possible to add an initiator in an amount sufficient to ensure the hardening of the coating film surface to suppress the change in film thickness after developing residue, and effectively reduce the internal friction of the coating film. Photocurability is preferable in terms of being easy to adjust so that the amount of line width shift does not become too large.
紫外線吸收劑之波長365 nm下之透過率可製備紫外線吸收劑之0.002質量%丙二醇單甲醚乙酸酯溶液,使用紫外可見近紅外分光光度計(例如日本分光股份有限公司之V-7100)測定該0.002質量%丙二醇單甲醚乙酸酯溶液。The transmittance of the ultraviolet absorber at a wavelength of 365 nm can be prepared with a 0.002% by mass propylene glycol monomethyl ether acetate solution of the ultraviolet absorber, and measured using a UV-visible-near-infrared spectrophotometer (such as V-7100 of JASCO Co., Ltd.) This 0.002 mass % propylene glycol monomethyl ether acetate solution.
本發明所使用之紫外線吸收劑於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率更佳為42%以下,進而較佳為40%以下。The transmittance of the ultraviolet absorber used in the present invention at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution is more preferably 42% or less, and more preferably 40% or less.
就獲得本發明之效果之方面而言,本發明所使用之紫外線吸收劑較佳為於25℃下之感光性著色樹脂組合物所使用之溶劑中之溶解度為1質量%以上者。 本發明所使用之紫外線吸收劑可為於25℃下之丙二醇單甲醚乙酸酯中之溶解度為1質量%以上者。 From the viewpoint of obtaining the effect of the present invention, the ultraviolet absorber used in the present invention is preferably one whose solubility in the solvent used for the photosensitive colored resin composition at 25° C. is 1% by mass or more. The ultraviolet absorber used in the present invention may have a solubility in propylene glycol monomethyl ether acetate at 25° C. of 1% by mass or more.
作為本發明所使用之紫外線吸收劑,例如可例舉如下化合物作為適宜者:2-(2-羥基-5-第三丁基苯基)-2H-苯并三唑、2-(2-羥基-5-第三辛基苯基)-2H-苯并三唑、2-[4-[(2-羥基-3-(2'-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三𠯤、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚、2-羥基-4-辛氧基二苯甲酮、2-(2-羥基-5-甲基苯基)-2H-苯并三唑、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑、2,2'-二羥基-4-甲氧基二苯甲酮、2-(2-羥基-5-甲基丙烯醯氧基乙基苯基)-2H-苯并三唑、(2-羥基-3-十二烷基-5-甲基苯基)苯并三唑等。 作為市售品,例如可例舉:TinuvinPS、Tinuvin329、Tinuvin405、Tinuvin477、Tinuvin479、Tinuvin571、Tinuvin928(以上為BASF製造)、Kemisorb12、Kemisorb71、Kemisorb71D、Kemisorb73、Kemisorb111(以上為Chemipro Kasei製造)、RUVA-93(以上為大塚化學製造)等。 As the ultraviolet absorber used in the present invention, for example, the following compounds can be cited as suitable ones: 2-(2-hydroxyl-5-tert-butylphenyl)-2H-benzotriazole, 2-(2-hydroxyl -5-tertiary octylphenyl)-2H-benzotriazole, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl] -4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethanone, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl) -4,6-bis(4-phenylphenyl)-1,3,5-trimethanone, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-benzene ethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-hydroxy-4-octyloxybenzophenone, 2-(2-hydroxy-5-methylbenzene base)-2H-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-dihydroxy-4- Methoxybenzophenone, 2-(2-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, (2-hydroxy-3-dodecyl-5- Methylphenyl) benzotriazole, etc. As commercially available items, for example, TinuvinPS, Tinuvin329, Tinuvin405, Tinuvin477, Tinuvin479, Tinuvin571, Tinuvin928 (the above are manufactured by BASF), Kemisorb12, Kemisorb71, Kemisorb71D, Kemisorb73, Kemisorb111 (the above are manufactured by Chemipro Kasei), RUVA-93 (The above are manufactured by Otsuka Chemical), etc.
於本發明中,紫外線吸收劑可單獨使用1種,或可混合使用2種以上。 再者,即便於選擇使用於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率為45%以下之紫外線吸收劑之情形時,亦可混合使用2種以上。即,本發明所使用之紫外線吸收劑即便包含單獨之於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率超過45%者,亦可混合2種以上,於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率若為45%以下,則可使用該等混合物之紫外線吸收劑。 In the present invention, the ultraviolet absorbent may be used alone or in combination of two or more. In addition, even when selecting and using an ultraviolet absorber having a transmittance of 45% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, two or more types may be used in combination. That is, even if the ultraviolet absorber used in the present invention has a transmittance of more than 45% at a wavelength of 365 nm in a 0.002 mass % propylene glycol monomethyl ether acetate solution alone, two or more types may be mixed to form a 0.002 mass % propylene glycol monomethyl ether acetate solution. If the transmittance at a wavelength of 365 nm in % propylene glycol monomethyl ether acetate solution is 45% or less, the ultraviolet absorber of the mixture can be used.
上述紫外線吸收劑之含量就獲得線寬抑制效果且以良好地進行硬化之方式調整光硬化性之目的而言,相對於感光性著色樹脂組合物之固形物成分總量,通常可為0.2質量%~4.0質量%之範圍內,較佳為0.3質量%~3.0質量%之範圍內,更佳為0.5質量%~2.0質量%之範圍內。 再者,固形物成分係溶劑以外之全部成分,亦包括液狀之光聚合性化合物等。 The content of the above-mentioned ultraviolet absorber is usually 0.2% by mass relative to the total solid content of the photosensitive colored resin composition for the purpose of obtaining the line width suppression effect and adjusting the photocurability so that the curing progresses favorably. It is within the range of ∼4.0% by mass, preferably within the range of 0.3% by mass to 3.0% by mass, more preferably within the range of 0.5% by mass to 2.0% by mass. In addition, the solid content refers to all components other than a solvent, and also includes a liquid photopolymerizable compound and the like.
又,就獲得線寬抑制效果且以良好地進行硬化之方式調整光硬化性之目的而言,紫外線吸收劑之合計質量相對於光起始劑與紫外線吸收劑之合計質量之比率較佳為2.0質量%~20.0質量%之範圍內,更佳為4.0質量%~18.0質量%之範圍內。In addition, for the purpose of obtaining the line width suppression effect and adjusting the photocurability in a manner to perform curing well, the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably 2.0 It is in the range of mass % - 20.0 mass %, More preferably, it is in the range of 4.0 mass % - 18.0 mass %.
[色材] 為了製成能夠形成抑制高溫加熱步驟前後之色度變化或亮度降低、使最終獲得之著色層之亮度變得良好並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層的感光性著色樹脂組合物,本發明中之色材含有三芳基甲烷系染料之色澱色材。 <三芳基甲烷系染料之色澱色材> 三芳基甲烷系染料之色澱色材就耐熱性及耐光性優異、達成彩色濾光片之高亮度化之方面而言,較佳為三芳基甲烷系染料與多酸之色澱色材。作為三芳基甲烷系染料之色澱色材,其中較佳為選自下述通式(1)所表示之色材、及下述通式(2)所表示之色材中之1種以上,就形成分子聚集狀態、表現出更優異之耐熱性、能夠達成高亮度之方面而言,較佳為下述通式(1)所表示之色材。 [color material] In order to form a photosensitive coloring layer that can suppress changes in chromaticity or decrease in brightness before and after the high-temperature heating step, improve the brightness of the finally obtained colored layer, and suppress changes in film thickness before and after development by thinner line widths The coloring resin composition, the coloring material in the present invention contains a lake coloring material of a triarylmethane dye. <Color material for triarylmethane-based dyes> The lake material of triarylmethane dyes is preferably a lake material of triarylmethane dyes and polyacids in terms of excellent heat resistance and light resistance, and high brightness of color filters. As the color material of the lake of triarylmethane dyes, preferably one or more selected from the color materials represented by the following general formula (1) and the color materials represented by the following general formula (2), In terms of forming a molecular aggregation state, exhibiting more excellent heat resistance, and being able to achieve high brightness, the color material represented by the following general formula (1) is preferable.
[化4] (通式(1)中,A為與N直接鍵結之碳原子不具有π鍵之a價之有機基,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基、或具有該脂肪族烴基之芳香族基,碳鏈中可含有雜原子。B c-表示c價之多酸陰離子。R i~R v各自獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基,R ii與R iii、R iv與R v可鍵結而形成環結構。R vi及R vii各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基。Ar 1表示可具有取代基之二價芳香族基。存在複數個之R i~R vii及Ar 1分別可相同亦可不同。 a及c表示2以上之整數,b及d表示1以上之整數。f及g表示0以上4以下之整數。存在複數個之f及g分別可相同亦可不同) [chemical 4] (In general formula (1), A is an a-valent organic group that does not have a valence of a carbon atom directly bonded to N, and the organic group represents an aliphatic group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N. A hydrocarbon group, or an aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms in the carbon chain. B c- represents a c-valent polyacid anion. R i ~ R v each independently represent a hydrogen atom, an alkane that may have a substituent R ii and R iii , R iv and R v may be bonded to form a ring structure. R vi and R vii each independently represent an alkyl group that may have a substituent, an alkyl group that may have a substituent An alkoxy group, a halogen atom or a cyano group. Ar 1 represents a divalent aromatic group that may have a substituent. There are a plurality of R i ~ R vii and Ar 1 may be the same or different. a and c represent 2 or more b and d represent integers of 1 or more. f and g represent integers of 0 to 4. Plural f and g may be the same or different)
[化5] (通式(2)中,R I~R VI各自獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基,R I與R II、R III與R IV、R V與R VI可鍵結而形成環結構。R VII及R VIII各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基。Ar 2表示可具有取代基之二價芳香族雜環基,存在複數個之R I~R VIII及Ar 2分別可相同亦可不同。E m-表示m價之多酸陰離子。 m表示2以上之整數。k及l表示0以上4以下之整數。存在複數個之k及l分別可相同亦可不同) [chemical 5] (In general formula (2), R I to R VI each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, R I and R II , R III and R IV , R V May be bonded with R VI to form a ring structure. R VII and R VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group. Ar 2 represents a group that may have a substituent For the divalent aromatic heterocyclic group, there are multiple R I ~ R VIII and Ar 2 which can be the same or different. E m- represents an m-valent polyacid anion. m represents an integer of 2 or more. k and l represent Integers from 0 to 4. Plural k and l may be the same or different)
上述通式(1)所表示之色材包含二價以上之陰離子與二價以上之陽離子,因此於該色材之凝集體中,陰離子與陽離子並非簡單地以1分子對1分子進行離子鍵結,而可形成複數個分子經由離子鍵聚集之分子聚集體,因此表觀分子量與先前之色澱顏料之分子量相比明顯增大。推定藉由此種分子聚集體之形成,固體狀態下之凝集力進一步提高,降低熱運動,能夠抑制離子對之解離或陽離子部之分解,與先前之色澱顏料相比不易退色。The color material represented by the above-mentioned general formula (1) contains anion with a divalent or higher valence and a cation with a divalent or higher valence. Therefore, in the aggregate of the color material, the anion and the cation are not simply ionically bonded by one molecule to one molecule. , and can form a molecular aggregate in which multiple molecules are aggregated through ionic bonds, so the apparent molecular weight is significantly increased compared with the molecular weight of the previous lake pigment. It is estimated that through the formation of such molecular aggregates, the cohesive force in the solid state is further improved, thermal movement is reduced, the dissociation of ion pairs or the decomposition of cationic parts can be suppressed, and it is less likely to fade than previous lake pigments.
上述通式(1)中之A係與N(氮原子)直接鍵結之碳原子不具有π鍵之a價之有機基,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基、或具有該脂肪族烴基之芳香族基,碳鏈中可含有O(氧原子)、S(硫原子)、N(氮原子)等雜原子。即,該有機基表示至少於與N直接鍵結之末端具有飽和脂肪族烴基且碳鏈中可含有O、S、N等雜原子之脂肪族烴基、或於與N直接鍵結之末端具有脂肪族烴基且碳鏈中可含有O、S、N等雜原子之芳香族基。由於與N直接鍵結之碳原子不具有π鍵,故而陽離子性之顯色部位所具有之色調或透過率等顏色特性不會受到連結基A或其他顯色部位之影響,而能夠保持與單體同樣之顏色。A in the above-mentioned general formula (1) is an organic group having a valency of a valence not having a π bond to a carbon atom directly bonded to N (nitrogen atom). The aliphatic hydrocarbon group of the hydrocarbon group, or the aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms such as O (oxygen atom), S (sulfur atom), and N (nitrogen atom) in the carbon chain. That is, the organic group means at least an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end directly bonded to N and may contain heteroatoms such as O, S, N in the carbon chain, or having an aliphatic hydrocarbon group at the end directly bonded to N. An aromatic group that is an aromatic hydrocarbon group and can contain heteroatoms such as O, S, and N in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as hue or transmittance of the cationic color-developing part will not be affected by the linking group A or other color-developing parts, and can be maintained with a single Body the same color.
於A中,關於至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基,只要與N直接鍵結之末端之碳原子不具有π鍵,則可為直鏈、支鏈或環狀之任一種,末端以外之碳原子可具有不飽和鍵,亦可具有取代基,碳鏈中可包含O、S、N。例如,可包含羰基、羧基、氧羰基、醯胺基等,氫原子可進而被取代為鹵素原子等。 又,於A中,上述具有脂肪族烴基之芳香族基可例舉含有至少於與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基的單環或多環芳香族基,可具有取代基,可為包含O、S、N之雜環。 其中,就骨架之堅牢性之方面而言,A較佳為包含環狀之脂肪族烴基或芳香族基。 作為環狀之脂肪族烴基,可例舉包含環己烷、環戊烷、降𦯉烷、聯環[2.2.2]辛烷、三環[5.2.1.0 2,6]癸烷、金剛烷之基等。又,作為芳香族基,例如可例舉包含苯環、萘環之基等。例如,於A為二價有機基之情形時,可例舉碳數1~20之直鏈、支鏈、或環狀之伸烷基或者苯二甲基等取代有2個碳數1~20之伸烷基之芳香族基等。 In A, regarding the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, as long as the carbon atom at the terminal directly bonded to N does not have a π bond, it may be straight chain, branched or cyclic In either shape, the carbon atoms other than the terminal may have unsaturated bonds or substituents, and the carbon chain may contain O, S, and N. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amido group, etc. may be included, and a hydrogen atom may be further substituted with a halogen atom, etc. Also, in A, the above-mentioned aromatic group having an aliphatic hydrocarbon group can be, for example, a monocyclic or polycyclic aromatic group containing an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, and may have a substitution The group can be a heterocycle containing O, S, N. Among them, in terms of the fastness of the skeleton, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group. Examples of the cyclic aliphatic hydrocarbon group include those containing cyclohexane, cyclopentane, nor-alkane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0 2,6 ]decane, and adamantane. Base etc. Moreover, as an aromatic group, the group containing a benzene ring, a naphthalene ring, etc. are mentioned, for example. For example, when A is a divalent organic group, it can be substituted by two straight-chain, branched, or cyclic alkylene groups or xylylene groups having 1-20 carbon atoms. Aromatic groups of alkylene groups, etc.
於本發明中,就兼顧堅牢性與分子運動之自由度、提高耐熱性之方面而言,較佳為A為具有2個以上之環狀脂肪族烴基、於與N直接鍵結之末端具有飽和脂肪族烴基、碳鏈中可包含O、S、N之脂肪族烴基。A更佳為具有2個以上之伸環烷基、於與N直接鍵結之末端具有飽和脂肪族烴基、碳鏈中可包含O、S、N之脂肪族烴基,其中,進而較佳為具有2個以上之環狀脂肪族烴基藉由直鏈或支鏈之脂肪族烴基連結而成之結構。 存在2個以上之環狀脂肪族烴基分別可相同亦可不同,例如可例舉與上述環狀之脂肪族烴基相同者,其中較佳為環己烷、環戊烷。 In the present invention, in terms of both fastness and freedom of molecular movement, and improving heat resistance, it is preferable that A has two or more cyclic aliphatic hydrocarbon groups, and has a saturation at the end directly bonded to N Aliphatic hydrocarbon group, an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain. A is more preferably an aliphatic hydrocarbon group having two or more cycloalkylene groups, a saturated aliphatic hydrocarbon group at the end directly bonded to N, and an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain. A structure in which two or more cyclic aliphatic hydrocarbon groups are linked by linear or branched aliphatic hydrocarbon groups. The two or more cyclic aliphatic hydrocarbon groups may be the same or different, for example, the same ones as the above-mentioned cyclic aliphatic hydrocarbon groups, among which cyclohexane and cyclopentane are preferable.
於本發明中,就耐熱性之方面而言,其中上述A較佳為下述通式(1a)所表示之取代基。In the present invention, the aforementioned A is preferably a substituent represented by the following general formula (1a) in terms of heat resistance.
[化6] (通式(1a)中,R xi表示可具有碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基作為取代基之碳數1以上3以下之伸烷基,R xii及R xiii各自獨立地表示碳數1以上4以下之烷基、或碳數1以上4以下之烷氧基,p表示1以上3以下之整數,q及r各自獨立地表示0以上4以下之整數。於R xi、R xii、R xiii及r存在複數個之情形時,該存在複數個之R xi、R xii、R xiii及r互相可相同亦可不同) [chemical 6] (In the general formula (1a), R xi represents an alkylene group with a carbon number of 1 to 4 and an alkyl group or an alkoxy group with a carbon number of 1 to 4 as a substituent, and R xii and R xiii each independently represent an alkyl group with 1 to 4 carbon atoms, or an alkoxy group with 1 to 4 carbon atoms, p represents an integer from 1 to 3, and q and r each independently represent 0 to 4 inclusive Integers. When Rxi, Rxii , Rxiii , and r exist in plural, the plural Rxi , Rxii , Rxiii , and r may be the same or different from each other )
就堅牢性與顯色部位之熱運動之兼顧優異、耐熱性提高之方面而言,較佳為R xi中之碳數1以上3以下之伸烷基。作為此種伸烷基,可例舉:亞甲基、伸乙基、伸丙基等,其中較佳為亞甲基或伸乙基,更佳為亞甲基。 作為碳數1以上4以下之烷基,可例舉:甲基、乙基、丙基、丁基,可為直鏈狀,亦可具有支鏈。 又,作為碳數1以上4以下之烷氧基,可例舉:甲氧基、乙氧基、丙氧基、丁氧基,可為直鏈狀,亦可具有支鏈。 It is preferably an alkylene group having 1 or more and 3 or less carbon atoms in R xi in terms of excellent balance between fastness and thermal movement of the color-developing site and improved heat resistance. Such an alkylene group may, for example, be a methylene group, an ethylidene group or a propylidene group, among which a methylene group or an ethylidene group is preferable, and a methylene group is more preferable. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, or a butyl group, which may be linear or branched. Moreover, examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched.
R xii及R xiii中之碳數1以上4以下之烷基、及碳數1以上4以下之烷氧基可例舉與上述R xi可具有之取代基相同者。 The alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms in R xii and R xiii include the same substituents as the substituents that R xi may have above.
於通式(1a)中,就耐熱性之方面而言,較佳為環己烷(伸環己基)為2個以上4個以下,即p為1以上3以下,其中更佳為p為1以上2以下。 又,伸環己基所具有之取代基R xii及R xiii之取代數並無特別限定,就耐熱性之方面而言,較佳為1個以上3個以下,更佳為1個以上2個以下。即較佳為q及r為1以上3以下之整數,較佳為q及r為1以上2以下之整數。 In the general formula (1a), in terms of heat resistance, the number of cyclohexane (cyclohexylene) is preferably 2 to 4, that is, p is 1 to 3, and p is 1 more preferably Above 2 and below. Also, the number of substitutions of the substituents R xii and R xiii of the cyclohexylene group is not particularly limited, but is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less in terms of heat resistance. . That is, q and r are preferably integers of 1 to 3, and q and r are preferably integers of 1 to 2.
作為此種連結基A之適宜之具體例,可例舉以下者,但不限定於該等。Suitable specific examples of such a linking group A include the following, but are not limited thereto.
[化7] [chemical 7]
R i~R v中之烷基並無特別限定。例如可例舉碳數1~20之直鏈、支鏈狀或環狀之烷基等,其中可例舉為碳數為1~8之直鏈或支鏈之烷基,就亮度及耐熱性之方面而言,可例舉為碳數為1~5之直鏈或支鏈之烷基,且可例舉R i~R v中之烷基為乙基或甲基。作為烷基可具有之取代基,並無特別限定,例如可例舉:芳基、鹵素原子、羥基、烷氧基等,作為經取代之烷基,可例舉如苄基之芳烷基等。 R i~R v中之芳基並無特別限定。例如可例舉:苯基、萘基等。作為芳基可具有之取代基,例如可例舉:烷基、鹵素原子、烷氧基、羥基等。 其中,就化學穩定性之方面而言,作為R i~R v,較佳為各自獨立為氫原子、碳數1~5之烷基、苯基,或R ii與R iii、R iv與R v鍵結而形成吡咯啶環、哌啶環、嗎啉環。 The alkyl groups in R i to R v are not particularly limited. For example, straight chain, branched or cyclic alkyl groups with 1 to 20 carbons can be exemplified, among which straight chain or branched alkyls with 1 to 8 carbons can be exemplified. In terms of brightness and heat resistance On the other hand, it may be a linear or branched alkyl group having 1 to 5 carbon atoms, and the alkyl group in R i to R v may be ethyl or methyl. The substituent that the alkyl group may have is not particularly limited, for example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, etc., and the substituted alkyl group includes an aralkyl group such as a benzyl group, etc. . The aryl group in R i to R v is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. As a substituent which an aryl group may have, an alkyl group, a halogen atom, an alkoxyl group, a hydroxyl group etc. are mentioned, for example. Among them, in terms of chemical stability, R i to R v are preferably each independently a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group, or R ii and R iii , R iv and R v is bonded to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.
就耐熱性之方面而言,較佳為R ii~R v中之至少一者為可具有取代基之環烷基、或可具有取代基之芳基。認為藉由R ii~R v中之至少一者具有環烷基、或芳基,由於立體阻礙產生之分子間相互作用降低,故而能夠抑制顯色部位對熱之影響,因此耐熱性優異。 In terms of heat resistance, at least one of R ii to R v is preferably a cycloalkyl group which may have a substituent or an aryl group which may have a substituent. It is considered that when at least one of R ii to R v has a cycloalkyl group or an aryl group, the intermolecular interaction due to steric hindrance is reduced, so that the effect of heat on the color-developing site can be suppressed, and thus the heat resistance is excellent.
就耐熱性之方面而言,較佳為R ii~R v中之至少一者為下述通式(1b)或下述通式(1c)所表示之取代基。 In terms of heat resistance, at least one of R ii to R v is preferably a substituent represented by the following general formula (1b) or the following general formula (1c).
[化8] (通式(1b)中,R xiv、R xv、及R xvi各自獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [chemical 8] (In general formula (1b), R xiv , R xv , and R xvi each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 4 that may have a substituent, or an alkyl group with a carbon number of 1 to 4 that may have a substituent the following alkoxy)
[化9] (通式(1c)中,R xvii、R xviii、及R xix各自獨立地表示氫原子、可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基) [chemical 9] (In general formula (1c), R xvii , R xviii , and R xix each independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 4 that may have a substituent, or an alkyl group with a carbon number of 1 to 4 that may have a substituent the following alkoxy)
作為R xiv、R xv、R xvi、R xvii、R xviii、及R xix中之碳數1以上4以下之烷基,可例舉:甲基、乙基、丙基、丁基,可為直鏈狀,亦可具有支鏈。又,作為碳數1以上4以下之烷氧基,可例舉:甲氧基、乙氧基、丙氧基、丁氧基,可為直鏈狀,亦可具有支鏈。 作為上述烷基及烷氧基可具有之取代基,可例舉:鹵素原子、羥基等。 Examples of alkyl groups having 1 to 4 carbon atoms in R xiv , R xv , R xvi , R xvii , R xviii , and R xix include methyl, ethyl, propyl, and butyl, which may be straight Chain, may also have branched chain. Moreover, examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched. As a substituent which the said alkyl group and alkoxy group may have, a halogen atom, a hydroxyl group, etc. are mentioned.
於具有上述通式(1b)所表示之取代基之情形時,就耐熱性之方面而言,較佳為R xiv、R xv、及R xvi之至少一者為可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基,更佳為R xiv及R xv之至少一者為可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基。 In the case of having a substituent represented by the above general formula (1b), in terms of heat resistance, at least one of R xiv , R xv , and R xvi is preferably 1 carbon number that may have a substituent The above-mentioned alkyl group of 4 or less, or an alkoxy group having a carbon number of 1 or more and 4 or less which may have a substituent, more preferably at least one of R xiv and R xv is an alkyl group having a carbon number of 1 or more and no more than 4 which may have a substituent group, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
又,於具有上述通式(1c)所表示之取代基之情形時,就耐熱性之方面而言,較佳為R xvii、R xviii、及R xix之至少一者為可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基,更佳為R xvii及R xviii之至少一者為可具有取代基之碳數1以上4以下之烷基、或可具有取代基之碳數1以上4以下之烷氧基。 Also, when having a substituent represented by the above-mentioned general formula (1c), it is preferable that at least one of R xvii , R xviii , and R xix is a carbon that may have a substituent in terms of heat resistance. An alkyl group with a number of 1 to 4, or an alkoxy group with a carbon number of 1 to 4 that may have a substituent, more preferably at least one of R xvii and R xviii has a carbon number of 1 to 4 that may have a substituent an alkyl group, or an alkoxy group having 1 to 4 carbon atoms which may have a substituent.
R vi及R vii各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基。作為R vi及R vii中之烷基,並無特別限定,較佳為碳數為1以上8以下之直鏈、或具有支鏈之烷基,更佳為碳數為1以上4以下之烷基。作為碳數1以上4以下之烷基,可例舉:甲基、乙基、丙基、丁基,可為直鏈狀,亦可具有支鏈。作為烷基可具有之取代基,並無特別限定,例如可例舉:芳基、鹵素原子、羥基、烷氧基等。 又,作為R vi及R vii中之烷氧基,並無特別限定,較佳為碳數為1以上8以下之直鏈、或具有支鏈之烷氧基,更佳為碳數為1以上4以下之烷氧基。作為碳數1以上4以下之烷氧基,可例舉:甲氧基、乙氧基、丙氧基、丁氧基,可為直鏈狀,亦可具有支鏈。作為烷氧基可具有之取代基,並無特別限定,例如可例舉:芳基、鹵素原子、羥基、烷氧基等。 作為R vi及R vii中之鹵素原子,例如可例舉:氟原子、氯原子、溴原子、碘原子。 R vi及R vii之取代數、即f及g分別獨立地表示0以上4以下之整數,其中較佳為0以上2以下,更佳為0以上1以下。存在複數個之f及g分別可相同亦可不同。 又,R vi及R vii可取代於具有三芳基甲烷骨架、或𠮿骨架內之共振結構之芳香環的任一部位,其中較佳為以-NR iiR iii或-NR ivR v所表示之胺基之取代位置為基準而取代於間位。 R vi and R vii each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. The alkyl group in R vi and R vii is not particularly limited, but is preferably a linear or branched alkyl group with a carbon number of 1 to 8, and more preferably an alkane with a carbon number of 1 to 4. base. The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, or a butyl group, which may be linear or branched. It does not specifically limit as a substituent which an alkyl group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned. Also, the alkoxy group in R vi and R vii is not particularly limited, but it is preferably a straight-chain or branched alkoxy group with a carbon number of 1 to 8, and more preferably a carbon number of 1 or more. Alkoxy groups of 4 or less. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, which may be linear or branched. It does not specifically limit as a substituent which an alkoxy group may have, For example, an aryl group, a halogen atom, a hydroxyl group, an alkoxy group etc. are mentioned. As a halogen atom in Rvi and Rvii , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The number of substitutions of R vi and R vii , that is, f and g each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1. Plural f and g may be the same or different. Also, R vi and R vii can be substituted with triarylmethane skeleton, or 𠮿 Any part of the aromatic ring of the resonance structure within the skeleton is preferably substituted at the meta position based on the substitution position of the amino group represented by -NR ii R iii or -NR iv R v .
Ar 1中之二價芳香族基並無特別限定。Ar 1中之芳香族基除了包含碳環之芳香族烴基以外,亦可為雜環基。作為芳香族烴基中之芳香族烴,除了苯環以外,可例舉:萘環、萘滿環、茚環、茀環、蒽環、菲環等縮合多環芳香族烴;聯苯、聯三苯、二苯基甲烷、三苯基甲烷、茋等鏈狀多環式烴。於該鏈狀多環式烴中,可如二苯基醚等般於鏈狀骨架中具有O、S、N。另一方面,作為雜環基中之雜環,可例舉:呋喃、噻吩、吡咯、㗁唑、噻唑、咪唑、吡唑等5員雜環;哌喃、吡喃酮、吡啶、吡喃酮、嗒𠯤、嘧啶、吡𠯤等6員雜環;苯并呋喃、苯并噻吩、吲哚、咔唑、香豆素、苯并吡喃酮、喹啉、異喹啉、吖啶、呔𠯤、喹唑啉、喹㗁啉等縮合多環式雜環。該等芳香族基可進而具有烷基、烷氧基、羥基、鹵素原子、及可經該等取代之苯基等作為取代基。 The divalent aromatic group in Ar 1 is not particularly limited. The aromatic group in Ar1 may be a heterocyclic group in addition to an aromatic hydrocarbon group containing a carbocycle. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, it can be exemplified: condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fenene ring, anthracene ring, phenanthrene ring, etc.; Benzene, diphenylmethane, triphenylmethane, stilbene and other chain polycyclic hydrocarbons. In this chain polycyclic hydrocarbon, O, S, and N may be included in the chain skeleton like diphenyl ether or the like. On the other hand, examples of the heterocyclic ring in the heterocyclic group include five-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, and pyrazole; pyran, pyrone, pyridine, and pyrone. , pyrimidine, pyrimidine, etc. 6-membered heterocycles; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, and benzofuran , quinazoline, quinoline and other condensed polycyclic heterocycles. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a phenyl group which may be substituted by these, etc. as a substituent.
1分子內存在複數個之R i~R vii及Ar 1可相同亦可不同。藉由R i~R vii及Ar 1之組合,可調整為所需之顏色。 Plural R i to R vii and Ar 1 present in one molecule may be the same or different. Through the combination of R i ~ R vii and Ar 1 , the required color can be adjusted.
A中之價數a為構成陽離子之顯色性陽離子部位之數,a為2以上之整數。於該色澱色材中,由於陽離子之價數a為2以上,故而耐熱性優異,其中,陽離子之價數a可為3以上。a之上限並無特別限定,就製造之容易性之方面而言,較佳為a為4以下,更佳為3以下。The valency a in A is the number of color-forming cation sites constituting the cation, and a is an integer of 2 or more. In this lake coloring material, since the valence a of the cation is 2 or more, heat resistance is excellent, and the valence a of the cation may be 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of manufacture.
通式(1)所表示之色材中之陽離子就耐熱性優異、容易抑制加熱時之顏色變化之方面而言,較佳為分子量為1200以上,較佳為1300以上。The cation in the color material represented by the general formula (1) has a molecular weight of preferably 1200 or more, more preferably 1300 or more, in terms of excellent heat resistance and easy suppression of color change during heating.
於通式(1)所表示之色材中,陰離子部(B c-)就高亮度且耐熱性優異之方面而言,為c價之多酸陰離子,且為二價以上之陰離子。 In the color material represented by the general formula (1), the anion part (B c- ) is a c-valent polyacid anion, and is a divalent or higher anion in terms of high brightness and excellent heat resistance.
作為複數個氧酸縮合而成之多酸陰離子,可為同多酸陰離子(M mO n) c-,亦可為雜多酸陰離子(X lM mO n) c-。上述離子式中,M表示多原子,X表示雜原子,m表示多原子之組成比,n表示氧原子之組成比。作為多原子M,例如可例舉:Mo、W、V、Ti、Nb等。又,作為雜原子X,例如可例舉:Si、P、As、S、Fe、Co等。又,亦可於一部分含有Na +或H +等抗衡陽離子。 其中,就耐熱性優異之方面而言,較佳為含有選自鎢(W)及鉬(Mo)中之1種以上元素之多酸。 作為此種多酸,例如可例舉:作為同多酸之鎢酸根離子[W 10O 32] 4-、鉬酸根離子[Mo 6O 19] 2-;或作為雜多酸之磷鎢酸根離子[PW 12O 40] 3-、[P 2W 18O 62] 6-、矽鎢酸根離子[SiW 12O 40] 4-、磷鉬酸根離子[PMo 12O 40] 3-、矽鉬酸根離子[SiMo 12O 40] 4-、磷鎢鉬酸根離子[PW 12-sMo sO 40] 3-(s為1以上11以下之整數)、[P 2W 18-tMo tO 62] 6-(t為1以上17以下之整數)、矽鎢鉬酸根離子[SiW 12-uMo uO 40] 4-(u為1以上11以下之整數)等。作為含有鎢(W)及鉬(Mo)之至少1種之多酸,就耐熱性之方面、及原料獲得之容易程度之方面而言,上述中較佳為雜多酸,更佳為進而含有磷(P)之雜多酸。 進而,就耐熱性之方面而言,進而較佳為磷鎢鉬酸根離子[PW 10Mo 2O 40] 3-、[PW 11Mo 1O 40] 3-、磷鎢酸根離子[PW 12O 40] 3-之任一種。 As a polyacid anion formed by condensation of multiple oxyacids, it can be an isopolyacid anion (M m O n ) c- , or a heteropolyacid anion (X l M m O n ) c- . In the above ionic formula, M represents a polyatom, X represents a heteroatom, m represents a composition ratio of a polyatom, and n represents a composition ratio of an oxygen atom. As polyatom M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as heteroatom X, Si, P, As, S, Fe, Co etc. are mentioned, for example. In addition, counter cations such as Na + or H + may be contained in a part. Among them, polyacids containing one or more elements selected from tungsten (W) and molybdenum (Mo) are preferable in terms of excellent heat resistance. As such polyacids, for example: tungstate ion [W 10 O 32 ] 4- , molybdate ion [Mo 6 O 19 ] 2- as isopolyacid; or phosphotungstate ion as heteropolyacid [PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , silicotungstate ion [SiW 12 O 40 ] 4- , phosphomolybdate ion [PMo 12 O 40 ] 3- , silicomolybdate ion [SiMo 12 O 40 ] 4- , Phosphotungstomolybdate ion [PW 12-s Mo s O 40 ] 3- (s is an integer between 1 and 11), [P 2 W 18-t Mo t O 62 ] 6 - (t is an integer ranging from 1 to 17), silicon tungsten molybdate ion [SiW 12-u Mo u O 40 ] 4- (u is an integer ranging from 1 to 11), etc. As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), in terms of heat resistance and ease of raw material acquisition, among the above, a heteropolyacid is preferred, and it is more preferred to further contain Phosphorus (P) heteropolyacid. Furthermore, in terms of heat resistance, phosphotungstate molybdate ion [PW 10 Mo 2 O 40 ] 3- , [PW 11 Mo 1 O 40 ] 3- , phosphotungstate ion [PW 12 O 40 ] any of 3- .
通式(1)中之b表示陽離子之數,d表示分子聚集體中之陰離子之數,b及d表示1以上之整數。於b為2以上之情形時,於分子聚集體中存在複數個之陽離子可為單獨1種,亦可組合2種以上。又,於d為2以上之情形時,於分子聚集體中存在複數個之陰離子可為單獨1種,亦可組合2種以上。b in the general formula (1) represents the number of cations, d represents the number of anions in molecular aggregates, and b and d represent integers of 1 or more. When b is 2 or more, a plurality of cations present in a molecular aggregate may be a single type or a combination of two or more types. Moreover, when d is 2 or more, the anion which exists in plural in a molecular aggregate may be a single type, and may combine 2 or more types.
再者,作為通式(1)所表示之色澱色材,例如可參考國際公開第2012/144520號說明書、國際公開第2018/003706號說明書進行製備。Furthermore, as the lake material represented by the general formula (1), for example, it can be prepared with reference to the specifications of International Publication No. 2012/144520 and International Publication No. 2018/003706.
另一方面,於通式(2)中,R I~R VI各自獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基,R I與R II、R III與R IV、R V與R VI可鍵結而形成環結構。R I~R VI分別可與上文所述之通式(1)之R i~R v相同。 於通式(2)中,R VII及R VIII各自獨立地表示可具有取代基之烷基、可具有取代基之烷氧基、鹵素原子或氰基,該等亦可與上文所述之通式(1)之R vi及R vii相同。 於通式(2)中,Ar 2表示可具有取代基之二價芳香族雜環基,該Ar 2可與上文所述之通式(1)之Ar 1中之芳香族雜環基相同。 又,於通式(2)中,E m-表示m價之多酸陰離子,該m價之多酸陰離子可與上文所述之通式(1)之c價之多酸陰離子相同。 On the other hand, in the general formula (2), R I to R VI each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and R I and R II , R III and R IV , R V and R VI may be bonded to form a ring structure. R I to R VI may be the same as R i to R v of the above general formula (1), respectively. In the general formula (2), R VII and R VIII each independently represent an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a halogen atom or a cyano group, and these may also be the same as those described above R vi and R vii of the general formula (1) are the same. In the general formula (2), Ar 2 represents a divalent aromatic heterocyclic group that may have a substituent, and the Ar 2 may be the same as the aromatic heterocyclic group in Ar 1 of the above-mentioned general formula (1) . Also, in the general formula (2), E m- represents an m-valent polyacid anion, and the m-valent polyacid anion may be the same as the c-valent polyacid anion of the above-mentioned general formula (1).
於通式(2)中,m表示陽離子之數及陰離子之數,表示2以上之整數。於通式(2)中存在複數個之陽離子可為單獨1種,亦可組合2種以上。又,陰離子亦為可為單獨1種,亦可組合2種以上。 又,通式(2)中之k及l可與上文所述之通式(1)之f及g相同。 再者,作為通式(2)所表示之色澱色材,例如可參考日本專利特開2017-16099號公報進行製備。 In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. A plurality of cations present in the general formula (2) may be alone or in combination of two or more. Moreover, an anion may be independent of 1 type, and may combine 2 or more types. Also, k and l in the general formula (2) may be the same as f and g in the above-mentioned general formula (1). Furthermore, as the lake material represented by the general formula (2), for example, it can be prepared with reference to JP-A-2017-16099.
又,作為本發明之感光性著色樹脂組合物所使用之三芳基甲烷系染料之色澱色材,不限於選自上述通式(1)所表示之色材及上述通式(2)所表示之色材中之1種以上,可適當選擇使用。 例如,可使用:日本專利特開2015-96947號公報、日本專利特開2016-27149號公報、及日本專利特開2017-16099號公報所記載之三芳基甲烷系染料之陽離子與如上述之各種多酸陰離子之色澱色材;或日本專利特開2015-96947號公報、日本專利特開2016-27149號公報、及日本專利特開2017-16099號公報所記載之三芳基甲烷系染料與多酸之色澱色材。 Also, as the lake color material of the triarylmethane dye used in the photosensitive colored resin composition of the present invention, it is not limited to the color material represented by the above general formula (1) and the color material represented by the above general formula (2). One or more of the color materials can be selected and used appropriately. For example, the cations of the triarylmethane dyes described in JP-A-2015-96947, JP-A-2016-27149, and JP-A-2017-16099 and the above-mentioned various Lake color material of polyacid anion; or the triarylmethane series dyes and poly Acid lake color material.
於本發明之感光性著色樹脂組合物中,上述三芳基甲烷系染料之色澱色材可單獨使用1種,或可組合使用2種以上。In the photosensitive colored resin composition of the present invention, the lake color material of the above-mentioned triarylmethane dye may be used alone or in combination of two or more.
<其他色材> 本發明所使用之色材含有三芳基甲烷系染料之色澱色材作為必需成分,於不損及本發明之效果之範圍內,為了調整色調,可進而組合使用其他色材。 作為其他色材,可單獨使用公知之顏料、染料、色澱色材等,或可將該等之2種以上混合使用。 <Other color materials> The coloring material used in the present invention contains a triarylmethane-based dye lake coloring material as an essential component, and other coloring materials may be used in combination to adjust the color tone within the range that does not impair the effect of the present invention. As other coloring materials, known pigments, dyes, lake coloring materials, etc. can be used alone, or two or more of them can be used in combination.
作為其他色材,其中,可適當地使用其他藍色色材、紫色色材、紅色色材,但不限定於該等。
作為其他藍色色材,有C.I.顏料藍15、15:1、15:2、15:3、15:4、15:6等公知之有機藍色顏料等。
作為紫色色材,有C.I.顏料紫1、14、15、19、23、29、32、33、36、37、38等公知之有機紫色顏料。
作為紅色或紫紅色色材,例如有國際公開第2020/071041號公報、日本專利特開2018-100323號公報、國際公開第2014/123125號公報等所記載等之𠮿染料及𠮿系染料之色澱色材等。
As other color materials, among them, other blue color materials, purple color materials, and red color materials can be suitably used, but are not limited to these. As other blue color materials, there are known organic blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6. As the purple color material, there are known organic purple pigments such as
<色材之含有比例>
於本發明之感光性著色樹脂組合物中,於不損及本發明之效果之範圍內,可於色材中進而含有三芳基甲烷系染料之色澱色材以外之其他色材,三芳基甲烷系染料之色澱色材之含有比例相對於色材總量,較佳為70質量%以上100質量%以下,進而較佳為80質量%以上100質量%以下,進而較佳為90質量%以上100質量%以下,進而更佳為95質量%以上100質量%以下。
<Containing ratio of color material>
In the photosensitive colored resin composition of the present invention, within the range that does not impair the effect of the present invention, other color materials other than triarylmethane-based dye lake color materials may be contained in the color material, triarylmethane The content ratio of the dye-based lake color material to the total color material is preferably from 70% by mass to 100% by mass, more preferably from 80% by mass to 100% by mass, and still more preferably at least 90% by
作為本發明所使用之色材之平均一次粒徑,於製成彩色濾光片之著色層之情形時,只要能夠實現所需之顯色即可,並無特別限定,依所使用之色材之種類而異,較佳為10~100 nm之範圍內,更佳為15~60 nm。藉由色材之平均一次粒徑為上述範圍,能夠將具備使用本發明之感光性著色樹脂組合物所製造之彩色濾光片之顯示裝置製成高對比度且高品質者。The average primary particle size of the color material used in the present invention is not particularly limited as long as the required color development can be achieved when the coloring layer of the color filter is made, depending on the color material used Depending on the type, it is preferably in the range of 10-100 nm, more preferably 15-60 nm. When the average primary particle diameter of a coloring material is the said range, the display device equipped with the color filter manufactured using the photosensitive colored resin composition of this invention can be made into a high-contrast and high-quality one.
又,感光性著色樹脂組合物中之色材之平均分散粒徑依所使用之色材之種類而異,較佳為10~100 nm之範圍內,更佳為15~60 nm之範圍內。 感光性著色樹脂組合物中之色材之平均分散粒徑係分散於至少含有溶劑之分散介質中之色材粒子之分散粒徑,可藉由雷射光散射粒度分佈計進行測定。作為利用雷射光散射粒度分佈計進行之粒徑之測定,可利用感光性著色樹脂組合物所使用之溶劑將感光性著色樹脂組合物適當稀釋(例如1000倍等)為能夠利用雷射光散射粒度分佈計測定之濃度,使用雷射光散射粒度分佈計(例如日機裝公司製造之Nanotrac粒度分佈測定裝置UPA-EX150),藉由動態光散射法於23℃進行測定。此處之平均分佈粒徑為體積平均粒徑。 Also, the average dispersed particle size of the color material in the photosensitive coloring resin composition varies depending on the type of color material used, and is preferably in the range of 10-100 nm, more preferably in the range of 15-60 nm. The average dispersed particle size of the color material in the photosensitive colored resin composition is the dispersed particle size of the color material particles dispersed in the dispersion medium containing at least a solvent, which can be measured by a laser light scattering particle size distribution meter. As the measurement of particle size using a laser light scattering particle size distribution meter, the photosensitive coloring resin composition can be appropriately diluted (for example, 1000 times, etc.) with the solvent used in the photosensitive coloring resin composition so that the laser light scattering particle size distribution can be used The concentration measured by the meter is measured at 23° C. by the dynamic light scattering method using a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average particle size distribution here is the volume average particle size.
本發明所使用之色材可藉由再結晶法、溶劑鹽磨法等公知之方法來製造。又,亦可將市售之色材進行微細化處理而使用。The color material used in the present invention can be produced by known methods such as recrystallization method and solvent salt milling method. Moreover, a commercially available color material can also be used by subjecting it to miniaturization treatment.
於本發明之感光性著色樹脂組合物中,色材之含量並無特別限定。色材之含量就分散性及分散穩定性之方面而言,相對於感光性著色樹脂組合物之固形物成分總量,通常為3質量%~65質量%之範圍內,較佳為4質量%~60質量%之範圍內,更佳為15質量%~60質量%之範圍內。若為上述下限值以上,則將感光性著色樹脂組合物塗佈為規定之膜厚(通常為1.0 μm~5.0 μm)時之著色層具有充分之色濃度。又,若為上述上限值以下,則能夠獲得保存穩定性優異並且具有充分之硬度或與基板之密接性之著色層。尤其是於形成色材濃度較高之著色層之情形時,色材之合計含量相對於感光性著色樹脂組合物之固形物成分總量,較佳為20質量%~65質量%之範圍內,更佳為30質量%~60質量%之範圍內。In the photosensitive colored resin composition of the present invention, the content of the color material is not particularly limited. The content of the coloring material is usually in the range of 3% by mass to 65% by mass, preferably 4% by mass, relative to the total solid content of the photosensitive colored resin composition in terms of dispersibility and dispersion stability It is in the range of ∼60% by mass, more preferably in the range of 15% by mass to 60% by mass. When it is more than the said lower limit, the colored layer when apply|coating the photosensitive colored resin composition to predetermined film thickness (normally 1.0 micrometer - 5.0 micrometer) has sufficient color density. Moreover, if it is below the said upper limit, the colored layer which is excellent in storage stability and has sufficient hardness or the adhesiveness with a board|substrate can be obtained. Especially when forming a colored layer with a high concentration of coloring materials, the total content of coloring materials is preferably in the range of 20% by mass to 65% by mass relative to the total solid content of the photosensitive colored resin composition. More preferably, it exists in the range of 30 mass % - 60 mass %.
[鹼可溶性樹脂] 本發明中之鹼可溶性樹脂具有酸性基,可自作為黏合劑樹脂發揮作用且可溶於圖案形成時所使用之鹼性顯影液中者中適當選擇而使用。 於本發明中,鹼可溶性樹脂可以酸值為40 mgKOH/g以上作為標準。 本發明中之較佳之鹼可溶性樹脂係具有酸性基、通常具有羧基之樹脂,具體而言,例如可例舉:具有羧基之丙烯酸系共聚物及具有羧基之苯乙烯-丙烯酸系共聚物等丙烯酸系樹脂、具有羧基之環氧(甲基)丙烯酸酯樹脂等。 [Alkali-soluble resin] The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that function as a binder resin and are soluble in an alkaline developer used for pattern formation. In the present invention, the alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acid groups and usually carboxyl groups. Specifically, for example, acrylic acid-based copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups may be mentioned. Resin, epoxy (meth)acrylate resin with carboxyl group, etc.
該等中尤佳者係於側鏈具有羧基、並且進而於側鏈具有乙烯性不飽和基等光聚合性官能基者。於含有光聚合性官能基之情形時,於製造彩色濾光片時之樹脂組合物之硬化步驟中,該鹼可溶性樹脂彼此、或該鹼可溶性樹脂與多官能單體等光聚合性化合物可形成交聯鍵。硬化膜之膜強度進一步提高,顯影耐性提高,又,硬化膜之熱收縮受到抑制,與基板之密接性變得優異。 將乙烯性不飽和鍵導入鹼可溶性樹脂中之方法自先前公知之方法中適當選擇即可。例如可例舉如下方法等:對鹼可溶性樹脂所具有之羧基加成分子內兼具環氧基與乙烯性不飽和鍵之化合物、例如(甲基)丙烯酸縮水甘油酯等,而對側鏈導入乙烯性不飽和鍵;或預先將具有羥基之結構單元導入共聚物中,加成分子內具有異氰酸基與乙烯性不飽和鍵之化合物,而對側鏈導入乙烯性不飽和鍵。 以下,存在將含有具有乙烯性不飽和鍵之基之單體(含有乙烯性不飽和基之單體)簡稱為乙烯性不飽和單體之情況。 Among them, those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are more preferable. In the case where a photopolymerizable functional group is contained, photopolymerizable compounds such as the alkali-soluble resins or the alkali-soluble resin and a polyfunctional monomer can be formed during the hardening step of the resin composition when producing a color filter. Crosslinks. The film strength of the cured film is further improved, the development resistance is improved, and the heat shrinkage of the cured film is suppressed, and the adhesiveness with the substrate becomes excellent. The method for introducing an ethylenically unsaturated bond into the alkali-soluble resin may be appropriately selected from previously known methods. For example, a method such as adding a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule to the carboxyl group of an alkali-soluble resin, such as glycidyl (meth)acrylate, etc., and introducing a side chain Ethylenically unsaturated bonds; or introduce structural units with hydroxyl groups into the copolymer in advance, add compounds with isocyanate groups and ethylenically unsaturated bonds in the molecule, and introduce ethylenically unsaturated bonds into the side chains. Hereinafter, a monomer containing a group having an ethylenically unsaturated bond (ethylenically unsaturated group-containing monomer) may be simply referred to as an ethylenically unsaturated monomer.
又,鹼可溶性樹脂就著色層之密接性優異之方面而言,較佳為進而具有烴環。藉由鹼可溶性樹脂含有作為大體積之基之烴環,硬化時之收縮受到抑制,與基板之間之剝離緩和,基板密接性提高。 作為此種烴環,可例舉:可具有取代基之脂肪族烴環、可具有取代基之芳香族烴環、及該等之組合,烴環可具有烷基、羰基、羧基、氧羰基、醯胺基、羥基、硝基、胺基、鹵素原子等取代基。 烴環可作為一價基含有,亦可作為二價以上之基含有。 Moreover, it is preferable that an alkali-soluble resin further has a hydrocarbon ring from the point which is excellent in the adhesiveness of a colored layer. Since the alkali-soluble resin contains a hydrocarbon ring as a bulky group, the shrinkage during curing is suppressed, the peeling between the substrate and the substrate is eased, and the substrate adhesion is improved. Such hydrocarbon rings include, for example, aliphatic hydrocarbon rings which may have substituents, aromatic hydrocarbon rings which may have substituents, and combinations thereof. The hydrocarbon rings may have alkyl groups, carbonyl groups, carboxyl groups, oxycarbonyl groups, Amide group, hydroxyl group, nitro group, amino group, halogen atom and other substituents. The hydrocarbon ring may be contained as a monovalent group, or may be contained as a divalent or higher group.
作為烴環之具體例,可例舉:環丙烷、環丁烷、環戊烷、環己烷、降𦯉烷、異𦯉烷、三環[5.2.1.0(2,6)]癸烷(二環戊烷)、金剛烷等脂肪族烴環;苯、萘、蒽、菲、茀等芳香族烴環;聯苯、聯三苯、二苯基甲烷、三苯基甲烷、茋等鏈狀多環、或Cardo結構(9,9-二芳基茀);該等基之一部分經取代基取代而成之基等。 作為上述取代基,可例舉:烷基、環烷基、烷基環烷基、羥基、羰基、硝基、胺基、鹵素原子等。 Specific examples of hydrocarbon rings include cyclopropane, cyclobutane, cyclopentane, cyclohexane, nor-alkane, iso-alkane, tricyclo[5.2.1.0(2,6)]decane (dicyclo[5.2.1.0(2,6)]decane, Cyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, stilbene and other aromatic hydrocarbon rings; biphenyl, terphenyl, diphenylmethane, triphenylmethane, stilbene and other chain poly A ring, or a Cardo structure (9,9-diaryl oxane); a group in which a part of these groups is substituted by a substituent, etc. As said substituent, an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a halogen atom, etc. are mentioned.
於作為烴環而含有脂肪族烴環之情形時,就著色層之耐熱性或密接性提高,並且所獲得之著色層之亮度提高之方面而言較佳。 又,於含有上述Cardo結構之情形時,就著色層之硬化性提高、抑制色材之退色、耐溶劑性(NMP(N-methylpyrrolidone,N-甲基吡咯啶酮)膨潤抑制)提高之方面而言尤佳。 When an aliphatic hydrocarbon ring is contained as a hydrocarbon ring, it is preferable in terms of improving the heat resistance or adhesiveness of the colored layer and improving the brightness of the obtained colored layer. In addition, when the above-mentioned Cardo structure is included, the curability of the colored layer is improved, the fading of the color material is suppressed, and the solvent resistance (NMP (N-methylpyrrolidone, N-methylpyrrolidone) swelling suppression) is improved. Yan Youjia.
含有具有羧基之結構單元之丙烯酸系共聚物、及具有羧基之苯乙烯-丙烯酸系共聚物等丙烯酸系樹脂例如為藉由公知之方法將含有羧基之乙烯性不飽和單體、及視需要能夠共聚之其他單體進行(共)聚合所獲得之(共)聚合物。 作為含有羧基之乙烯性不飽和單體,例如可例舉:(甲基)丙烯酸、乙烯基苯甲酸、馬來酸、馬來酸單烷基酯、富馬酸、伊康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基之單體與如馬來酸酐或鄰苯二甲酸酐、環己烷二羧酸酐之環狀酐之加成反應物、ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,作為羧基之前驅物,亦可使用馬來酸酐、伊康酸酐、檸康酸酐等含酐單體。其中,就共聚性或成本、溶解性、玻璃轉移溫度等方面而言,尤佳為(甲基)丙烯酸。 Acrylic resins such as an acrylic copolymer containing a structural unit having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group are obtained by, for example, copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and, if necessary, by a known method. A (co)polymer obtained by (co)polymerizing other monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , cinnamic acid, acrylic acid dimer, etc. Also, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω -Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as carboxyl group precursors. Among them, (meth)acrylic acid is particularly preferable in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.
本發明中之鹼可溶性樹脂較佳為含有具有羧基之結構單元與具有烴環之結構單元之丙烯酸系共聚物及苯乙烯-丙烯酸系共聚物等含有羧基之共聚物,更佳為含有具有羧基之結構單元、具有烴環之結構單元及具有乙烯性不飽和鍵之結構單元之丙烯酸系共聚物及苯乙烯-丙烯酸系共聚物等含有羧基之共聚物。The alkali-soluble resin in the present invention is preferably an acrylic copolymer containing a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring, and a copolymer containing a carboxyl group such as a styrene-acrylic copolymer, and more preferably a copolymer containing a carboxyl group. Carboxyl group-containing copolymers such as structural units, structural units having hydrocarbon rings and structural units having ethylenically unsaturated bonds, acrylic copolymers, and styrene-acrylic copolymers.
作為具有烴環之乙烯性不飽和單體,例如可例舉:(甲基)丙烯酸環己酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸異𦯉基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等,就顯影後之著色層之截面形狀於加熱處理中亦維持之效果較大之方面而言,較佳為使用選自(甲基)丙烯酸環己酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、及苯乙烯中之至少1種。Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include: cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid Isophthalate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development even during heat treatment. It is preferred to use at least one of cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and
該含有羧基之共聚物可進而含有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等具有酯基之結構單元等其他結構單元。具有酯基之結構單元不僅作為抑制著色樹脂組合物之鹼可溶性之成分發揮功能,而且亦作為提高相對於溶劑之溶解性、進而溶劑再溶解性之成分而發揮功能。This carboxyl group-containing copolymer may further contain other structural units such as structural units having ester groups such as methyl (meth)acrylate and ethyl (meth)acrylate. The structural unit which has an ester group functions not only as a component which suppresses the alkali solubility of a colored resin composition, but also functions as a component which improves solubility with respect to a solvent, and further solvent resolubility.
該含有羧基之共聚物可藉由適當調整各結構單元之添加量而製成具有所需之性能之鹼可溶性樹脂。 含有羧基之乙烯性不飽和單體之添加量就獲得良好之圖案之方面而言,相對於單體總量,較佳為5質量%以上,更佳為10質量%以上。另一方面,就抑制顯影後之圖案表面之膜粗糙等之方面而言,含有羧基之乙烯性不飽和單體之添加量相對於單體總量,較佳為50質量%以下,更佳為40質量%以下。 The carboxyl-containing copolymer can be prepared into an alkali-soluble resin with required properties by properly adjusting the addition amount of each structural unit. The amount of the carboxyl group-containing ethylenically unsaturated monomer added is preferably at least 5% by mass, more preferably at least 10% by mass, based on the total amount of monomers, from the viewpoint of obtaining a good pattern. On the other hand, in terms of suppressing film roughness on the surface of the pattern after development, the amount of ethylenically unsaturated carboxyl group-containing monomer added is preferably 50% by mass or less, more preferably 40% by mass or less.
又,於作為鹼可溶性樹脂而可更佳地使用之含有具有乙烯性不飽和鍵之結構單元之丙烯酸系共聚物及苯乙烯-丙烯酸系共聚物等含有羧基之共聚物中,兼具環氧基與乙烯性不飽和鍵之化合物相對於含有羧基之乙烯性不飽和單體之添加量,較佳為10質量%以上95質量%以下,更佳為15質量%以上90質量%以下。In addition, in carboxyl-containing copolymers such as acrylic copolymers containing structural units having ethylenically unsaturated bonds and styrene-acrylic copolymers that can be used more preferably as alkali-soluble resins, epoxy group The amount of the compound having an ethylenically unsaturated bond relative to the carboxyl group-containing ethylenically unsaturated monomer is preferably from 10% by mass to 95% by mass, more preferably from 15% by mass to 90% by mass.
含有羧基之共聚物之較佳之質量平均分子量(Mw)較佳為1,000~50,000之範圍,進而較佳為3,000~20,000。若為1,000以上,則硬化後之黏合劑功能提高,若為50,000以下,則於利用鹼性顯影液進行顯影時,圖案形成變得良好。The preferred mass average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. When it is 1,000 or more, the adhesive function after hardening improves, and when it is 50,000 or less, pattern formation will become favorable at the time of image development with an alkaline developing solution.
作為具有羧基之環氧(甲基)丙烯酸酯樹脂,並無特別限定,適合的是使環氧化合物與含有不飽和基之單羧酸之反應物與酸酐進行反應所獲得之環氧(甲基)丙烯酸酯化合物。 環氧化合物、含有不飽和基之單羧酸、及酸酐可自公知者中適當選擇使用。 作為具有羧基之環氧(甲基)丙烯酸酯樹脂,亦較佳為於分子內具有上述烴環,其中,就著色層之硬化性提高、抑制色材之退色、且著色層之殘膜率提高之方面而言,較佳為含有Cardo結構者。 具有羧基之環氧(甲基)丙烯酸酯樹脂可分別單獨使用1種,亦可併用兩種以上。 The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and an epoxy (meth)acrylate resin obtained by reacting an epoxy compound with a monocarboxylic acid containing an unsaturated group with an acid anhydride is suitable. ) acrylate compounds. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. As the epoxy (meth)acrylate resin having a carboxyl group, it is also preferable to have the above-mentioned hydrocarbon ring in the molecule. Among them, the curability of the colored layer is improved, the fading of the colored material is suppressed, and the residual film rate of the colored layer is improved. On the other hand, those containing a Cardo structure are preferable. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, and may use 2 or more types together.
鹼可溶性樹脂就相對於顯影液所使用之鹼性水溶液之顯影性(溶解性)之方面而言,較佳為選擇使用酸值為30 mgKOH/g以上者。鹼可溶性樹脂就相對於顯影液所使用之鹼性水溶液之顯影性(溶解性)之方面、及對基板之密接性之方面而言,較佳為酸值為40 mgKOH/g以上300 mgKOH/g以下,其中較佳為50 mgKOH/g以上280 mgKOH/g以下。As the alkali-soluble resin, it is preferable to select and use one having an acid value of 30 mgKOH/g or more in terms of developability (solubility) with respect to the alkaline aqueous solution used for the developing solution. The alkali-soluble resin preferably has an acid value of 40 mgKOH/g or more and 300 mgKOH/g in terms of developability (solubility) to the alkaline aqueous solution used in the developer and adhesion to the substrate Below, preferably 50 mgKOH/g or more and 280 mgKOH/g or less.
鹼可溶性樹脂之側鏈具有乙烯性不飽和基之情形時之乙烯性不飽和鍵當量就獲得硬化膜之膜強度提高且顯影耐性提高、與基板之密接性優異等效果之方面而言,較佳為100~2000之範圍,尤佳為140~1500之範圍。若該乙烯性不飽和鍵當量為2000以下,則顯影耐性或密接性優異。又,若為100以上,則能夠相對地增加上述具有羧基之結構單元、或具有烴環之結構單元等其他結構單元之比例,因此顯影性或耐熱性優異。 此處,乙烯性不飽和鍵當量係上述鹼可溶性樹脂中之相對於乙烯性不飽和鍵1莫耳之質量平均分子量,以下述數式(1)表示。 When the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferable in terms of obtaining effects such as increased film strength of the cured film, improved development resistance, and excellent adhesion to the substrate. It is in the range of 100-2000, more preferably in the range of 140-1500. When the ethylenically unsaturated bond equivalent is 2000 or less, it will be excellent in image development resistance and adhesiveness. Moreover, if it is 100 or more, since the ratio of other structural units, such as the structural unit which has the said carboxyl group, or the structural unit which has a hydrocarbon ring, can be relatively increased, it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent is the mass average molecular weight with respect to 1 mol of ethylenically unsaturated bond in the said alkali-soluble resin, and is represented by following numerical formula (1).
數式(1) 乙烯性不飽和鍵當量(g/mol)=W(g)/M(mol) (數式(1)中,W表示鹼可溶性樹脂之質量(g),M表示鹼可溶性樹脂W(g)中所含之乙烯性不飽和鍵之莫耳數(mol)) Mathematical formula (1) Ethylenic unsaturated bond equivalent (g/mol)=W(g)/M(mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g))
上述乙烯性不飽和鍵當量例如亦可依據JIS K 0070:1992所記載之碘值之試驗方法,測定鹼可溶性樹脂1 g所含之乙烯性不飽和鍵之數,藉此算出。The above-mentioned ethylenically unsaturated bond equivalent can also be calculated by measuring the number of ethylenically unsaturated bonds contained in 1 g of alkali-soluble resin according to the test method of iodine value described in JIS K 0070:1992, for example.
感光性著色樹脂組合物中所使用之鹼可溶性樹脂可單獨使用1種,亦可組合使用2種以上,其含量並無特別限制,相對於感光性著色樹脂組合物之固形物成分總量,鹼可溶性樹脂較佳為5質量%以上60質量%以下之範圍內,進而較佳為8質量%以上40質量%以下之範圍內。若鹼可溶性樹脂之含量為上述下限值以上,則可獲得充分之鹼性顯影性,又,若鹼可溶性樹脂之含量為上述上限值以下,則於顯影時能夠抑制膜粗糙或圖案之缺陷。The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more, and its content is not particularly limited. With respect to the total solid content of the photosensitive colored resin composition, the alkali The soluble resin is preferably within the range of 5% by mass to 60% by mass, and more preferably within the range of 8% by mass to 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is below the above upper limit, film roughness or pattern defects can be suppressed during development. .
[光聚合性化合物] 感光性著色樹脂組合物中所使用之光聚合性化合物只要藉由光起始劑而能夠聚合即可,並無特別限定,通常可適宜地使用具有2個以上乙烯性不飽和鍵之化合物,尤佳為具有2個以上丙烯醯基或甲基丙烯醯基之多官能(甲基)丙烯酸酯。 作為此種多官能(甲基)丙烯酸酯,自先前公知者中適當選擇使用即可。作為具體例,例如可例舉日本專利特開2013-029832號公報所記載者等。 [Photopolymerizable compound] The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by a photoinitiator, and usually a compound having two or more ethylenically unsaturated bonds can be suitably used, especially A polyfunctional (meth)acrylate having two or more acryl groups or methacryl groups is preferable. As such a polyfunctional (meth)acrylate, what is necessary is just to select suitably from well-known thing beforehand, and to use it. As a specific example, what is described in Unexamined-Japanese-Patent No. 2013-029832, etc. are mentioned, for example.
該等多官能(甲基)丙烯酸酯可單獨使用1種,亦可組合使用2種以上。又,於對本發明之感光性著色樹脂組合物要求優異之光硬化性(高感度)之情形時,多官能(甲基)丙烯酸酯較佳為具有3個(三官能)以上能夠聚合之乙烯性不飽和鍵者,較佳為三價以上之多元醇之聚(甲基)丙烯酸酯類或該等之二羧酸改性物,具體而言,較佳為:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯之琥珀酸改性物、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯之琥珀酸改性物、二季戊四醇六(甲基)丙烯酸酯等。These polyfunctional (meth)acrylates may be used alone or in combination of two or more. Also, when excellent photocurability (high sensitivity) is required for the photosensitive colored resin composition of the present invention, the polyfunctional (meth)acrylate preferably has three or more (trifunctional) vinylic resins capable of polymerizing. Those with unsaturated bonds are preferably poly(meth)acrylates of polyhydric alcohols with a valence of more than three or their modified dicarboxylic acids, specifically, trimethylolpropane tri(methyl)propane base) acrylate, pentaerythritol tri(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol Penta(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.
本發明中所使用之光聚合性化合物就能夠兼顧較高之顯影殘膜率與較細之線寬之方面而言,其中較佳為含有包含環氧烷之光聚合性化合物。 作為包含環氧烷之光聚合性化合物,較佳可例舉包含環氧乙烷及/或環氧丙烷之光聚合性化合物。於含有上述包含環氧烷之光聚合性化合物之情形時,推定自因氧抑制而喪失聚合活性之過氧自由基再生成具有活性之自由基,因此硬化性提高。 作為上述包含環氧烷之光聚合性化合物,可例舉:環氧烷改性季戊四醇三(甲基)丙烯酸酯、環氧烷改性季戊四醇四(甲基)丙烯酸酯、環氧烷改性二季戊四醇四(甲基)丙烯酸酯、環氧烷改性二季戊四醇五(甲基)丙烯酸酯、環氧烷改性二季戊四醇六(甲基)丙烯酸酯、環氧烷改性三羥甲基丙烷三(甲基)丙烯酸酯、及環氧烷改性甘油二(甲基)丙烯酸酯等,更具體而言,可例舉:環氧乙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改性季戊四醇五(甲基)丙烯酸酯、環氧乙烷改性二季戊四醇六(甲基)丙烯酸酯、環氧丙烷改性季戊四醇三(甲基)丙烯酸酯、環氧丙烷改性季戊四醇四(甲基)丙烯酸酯、環氧丙烷改性二季戊四醇六(甲基)丙烯酸酯、環氧乙烷改性甘油三(甲基)丙烯酸酯、環氧乙烷改性二甘油四(甲基)丙烯酸酯等。其中,更佳為包含環氧乙烷改性二甘油四(甲基)丙烯酸酯、環氧乙烷改性二季戊四醇六(甲基)丙烯酸酯。 The photopolymerizable compound used in the present invention preferably contains a photopolymerizable compound containing an alkylene oxide in terms of achieving both a high residual film rate after image development and a thin line width. As a photopolymerizable compound containing an alkylene oxide, Preferably, the photopolymerizable compound containing ethylene oxide and/or propylene oxide is mentioned. When the photopolymerizable compound containing the above-mentioned alkylene oxide is contained, active radicals are regenerated from peroxyl radicals which have lost their polymerization activity due to oxygen inhibition, so that curability is improved. Examples of the photopolymerizable compound containing alkylene oxide include: alkylene oxide-modified pentaerythritol tri(meth)acrylate, alkylene oxide-modified pentaerythritol tetra(meth)acrylate, alkylene oxide-modified di Pentaerythritol tetra(meth)acrylate, alkylene oxide modified dipentaerythritol penta(meth)acrylate, alkylene oxide modified dipentaerythritol hexa(meth)acrylate, alkylene oxide modified trimethylolpropane tri (Meth)acrylate, and alkylene oxide-modified glycerin di(meth)acrylate, etc., More specifically, ethylene oxide-modified trimethylolpropane tri(meth)acrylate , Ethylene oxide modified pentaerythritol penta(meth)acrylate, Ethylene oxide modified dipentaerythritol hexa(meth)acrylate, Propylene oxide modified pentaerythritol tri(meth)acrylate, Propylene oxide modified Pentaerythritol tetra(meth)acrylate, propylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified glycerol tri(meth)acrylate, ethylene oxide modified diglycerol tetra( Meth)acrylate, etc. Among them, it is more preferable to include ethylene oxide-modified diglycerin tetra(meth)acrylate and ethylene oxide-modified dipentaerythritol hexa(meth)acrylate.
光聚合性化合物可單獨使用1種,或可混合使用2種以上。
作為光聚合性化合物,可將包含環氧烷之光聚合性化合物與不含環氧烷之光聚合性化合物混合使用。
含有包含環氧烷之光聚合性化合物之情形時之含量相對於光聚合性化合物總量,較佳為3質量%~50質量%之範圍內,更佳為5質量%~30質量%之範圍內。
A photopolymerizable compound may be used individually by 1 type, or may mix and
感光性著色樹脂組合物中所使用之上述光聚合性化合物之含量並無特別限制,相對於感光性著色樹脂組合物之固形物成分總量較佳為5質量%~60質量%之範圍內,更佳為10質量%~40質量%之範圍內。若光聚合性化合物之含量為上述下限值以上,則光硬化充分進行,能夠抑制曝光部分顯影時之溶出,線寬偏移受到抑制,耐溶劑性變得良好,又,若光聚合性化合物之含量為上述上限值以下,則鹼性顯影性充分。The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but it is preferably in the range of 5% by mass to 60% by mass relative to the total solid content of the photosensitive colored resin composition. More preferably, it exists in the range of 10 mass % - 40 mass %. If the content of the photopolymerizable compound is more than the above-mentioned lower limit value, then the photocuring will proceed sufficiently, the elution during development of the exposed part can be suppressed, the deviation of the line width is suppressed, and the solvent resistance becomes good. In addition, if the photopolymerizable compound Alkali developability is sufficient if the content is below the above upper limit.
[光起始劑] 作為本發明之感光性著色樹脂組合物所使用之光起始劑,並無特別限制,可自先前已知之各種起始劑中組合使用1種或2種以上。 作為光起始劑,例如可例舉:二苯甲酮、N,N-二甲胺基二苯甲酮、4,4'-雙二乙胺基二苯甲酮(例如Hicure ABP,川口藥品製造)、4-甲氧基-4'-二甲胺基二苯甲酮等芳香族酮類;安息香甲醚等安息香醚類;乙基安息香等安息香類;2-(鄰氯苯基)-4,5-苯基咪唑二聚物等聯咪唑類;2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-㗁二唑等鹵甲基㗁二唑化合物;2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三𠯤等之甲基-S-三𠯤類;1,2-辛二酮-1-[4-(苯硫基)-,2-(鄰苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(鄰乙醯基肟)、日本專利特開2000-80068號公報、日本專利特開2001-233842號公報、日本專利特表2010-527339號公報、日本專利特表2010-527338號公報、日本專利特開2013-041153號公報等所記載之肟酯系光起始劑等肟酯類;2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮(例如Irgacure 907,BASF公司製造)、2-苄基-2-(二甲胺基)-1-(4-嗎啉基苯基)-1-丁酮(例如Irgacure 369,BASF公司製造)、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮(Irgacure 379EG,BASF公司製造)等α-胺基酮類;二乙基-9-氧硫𠮿等9-氧硫𠮿類。 其中,本發明所使用之光起始劑就感度優異之方面而言,較佳為包含選自肟酯類及α-胺基酮類中之至少1種,就圖案形成時之線寬調整與顯影耐性之觀點而言,較佳為α-胺基酮類。由於具有三級胺結構之α-胺基酮類於分子內具有作為氧抑止劑之三級胺結構,故而自起始劑產生之自由基不易因氧而失活,能夠提高感度,因此較佳。 又,作為光起始劑,就抑制水斑、且提高感度之方面而言,亦較佳為將肟酯類與α-胺基酮類組合使用。再者,水斑係指若使用提高鹼性顯影性之成分,則鹼性顯影後,於利用純水沖洗後產生如水浸染之痕跡之情況。此種水斑於後烘烤後會消失,因此製品並無問題,但於顯影後圖案化面之外觀檢查中,會作為斑點異常被檢測出,產生正常品與異常品不加區別之問題。因此,於外觀檢查中,若降低檢查裝置之檢查感度,則結果會引起最終之彩色濾光片製品之良率降低而成為問題。 又,作為光起始劑,就調整感度、抑制水斑、顯影耐性提高之方面而言,較佳為將選自肟酯類及α-胺基酮類中之至少1種與9-氧硫𠮿類加以組合。 [Photoinitiator] The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and may be used in combination of 1 or 2 or more types of previously known various initiators. As the photoinitiator, for example, benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (for example, Hicure ABP, Kawaguchi Pharmaceutical Co., Ltd. Manufacturing), 4-methoxy-4'-dimethylaminobenzophenone and other aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; 2-(o-chlorophenyl)- 4,5-phenylimidazole dimer and other biimidazoles; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl oxadiazoles Compounds; 2-(4-butoxy-naphthalene-1-yl)-4,6-bis-trichloromethyl-S-trichloromethyl-S-three sulfones and other methyl-S-three sulfides; 1,2-octanyl Ketone-1-[4-(phenylthio)-, 2-(o-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)- 9H-carbazol-3-yl]-,1-(o-acetyloxime), Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2010-527339 , Japanese Patent Publication No. 2010-527338, Japanese Patent Application Publication No. 2013-041153, etc. oxime esters such as oxime ester-based photoinitiators; 2-methyl-1-(4-methylthiobenzene base)-2-morpholinopropan-1-one (such as Irgacure 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1 -butanone (for example, Irgacure 369, manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene α-amino ketones such as base]-1-butanone (Irgacure 379EG, manufactured by BASF Corporation); diethyl-9-oxothiophenone 9-oxosulfur kind. Among them, the photoinitiator used in the present invention preferably contains at least one selected from the group consisting of oxime esters and α-amino ketones in terms of excellent sensitivity. From the viewpoint of development resistance, α-aminoketones are preferred. Since the α-aminoketones with a tertiary amine structure have a tertiary amine structure as an oxygen inhibitor in the molecule, the free radicals generated from the initiator are not easily inactivated by oxygen, and the sensitivity can be improved, so it is better . Also, as a photoinitiator, it is also preferable to use oxime esters and α-amino ketones in combination in terms of suppressing water spots and improving sensitivity. Furthermore, the water spot refers to the situation that if a component that improves the alkali developability is used, after the alkali development is rinsed with pure water, there will be traces such as water staining. This kind of water spots will disappear after post-baking, so there is no problem with the product, but in the visual inspection of the patterned surface after development, it will be detected as abnormal spots, causing the problem that normal products and abnormal products cannot be distinguished. Therefore, in the visual inspection, if the inspection sensitivity of the inspection device is lowered, the yield rate of the final color filter product will decrease as a result, which becomes a problem. In addition, as a photoinitiator, it is preferable to combine at least one selected from oxime esters and α-amino ketones with 9-oxysulfur in terms of adjusting sensitivity, suppressing water spots, and improving development resistance. 𠮿 Classes are combined.
本發明之感光性著色樹脂組合物中所使用之光起始劑之合計含量只要不損及本發明之效果,則無特別限制,相對於感光性著色樹脂組合物之固形物成分總量,較佳為0.1質量%~12.0質量%之範圍內,更佳為1.0質量%~8.0質量%之範圍內。若該含量為上述下限值以上,則光硬化充分進行,抑制曝光部分於顯影時溶出,耐溶劑性變得良好,另一方面,若為上述上限值以下,則能夠抑制所獲得之著色層因黃變引起之亮度之降低。 又,感光性著色樹脂組合物中所使用之上述光聚合性化合物與上述光起始劑之含有比例就抑制線寬偏移、耐溶劑性變得良好之方面,進而就提高顯影殘渣之抑制效果之方面而言,相對於上述光聚合性化合物100質量份,上述光起始劑之合計含有比例較佳為5質量份以上,更佳為10質量份以上,且較佳為40質量份以下,更佳為30質量份以下。 又,上述光起始劑之合計質量相對於上述光起始劑與上述紫外線吸收劑之合計質量之比率較佳為80質量%~98質量%之範圍內,更佳為82質量%~96質量%之範圍內。若該含量為上述下限值以上,則即便於紫外線吸收劑存在下亦能夠充分確保光硬化性,另一方面,若為上述上限值以下,則容易獲得紫外線吸收劑之線寬調整之效果。 The total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it does not impair the effect of the present invention. Preferably, it exists in the range of 0.1 mass % - 12.0 mass %, More preferably, it exists in the range of 1.0 mass % - 8.0 mass %. If the content is not less than the above-mentioned lower limit, the photocuring will proceed sufficiently, the elution of the exposed portion during development will be suppressed, and the solvent resistance will become good. On the other hand, if it is not more than the above-mentioned upper limit, the obtained coloring can be suppressed. The reduction of the brightness of the layer due to yellowing. In addition, the content ratio of the above-mentioned photopolymerizable compound and the above-mentioned photoinitiator used in the photosensitive coloring resin composition can suppress line width deviation and improve solvent resistance, and further improve the effect of suppressing development residue. On the other hand, relative to 100 parts by mass of the above-mentioned photopolymerizable compound, the total content ratio of the above-mentioned photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and preferably 40 parts by mass or less, More preferably, it is 30 mass parts or less. Also, the ratio of the total mass of the above-mentioned photoinitiator to the total mass of the above-mentioned photoinitiator and the above-mentioned ultraviolet absorber is preferably in the range of 80% by mass to 98% by mass, more preferably 82% by mass to 96% by mass % range. If the content is more than the above lower limit, sufficient photocurability can be ensured even in the presence of an ultraviolet absorber. On the other hand, if it is below the above upper limit, the effect of adjusting the line width of the ultraviolet absorber can be easily obtained. .
[溶劑] 作為本發明所使用之溶劑,只要為不與感光性著色樹脂組合物中之各成分進行反應且能夠溶解或分散該等之有機溶劑即可,並無特別限定。溶劑可單獨使用或組合使用2種以上。 作為溶劑之具體例,例如可例舉:甲醇、乙醇、N-丙醇、異丙醇、甲氧基醇、乙氧基醇等醇系溶劑;甲氧基乙氧基乙醇、乙氧基乙氧基乙醇等卡必醇系溶劑;乙酸乙酯、乙酸丁酯、甲氧基丙酸甲酯、甲氧基丙酸乙酯、乙氧基丙酸乙酯、乳酸乙酯、羥基丙酸甲酯、羥基丙酸乙酯、正丁基乙酸酯、異丁基乙酸酯、丁酸異丁酯、丁酸正丁酯、乳酸乙酯、環己醇乙酸酯等酯系溶劑;丙酮、甲基乙基酮、甲基異丁基酮、環己酮、2-庚酮等酮系溶劑;乙酸甲氧基乙酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基-3-甲基-1-丁酯、乙酸3-甲氧基丁酯、乙酸乙氧基乙酯等二醇醚乙酸酯系溶劑;乙酸甲氧基乙氧基乙酯、乙酸乙氧基乙氧基乙酯、丁基卡必醇乙酸酯(BCA)等卡必醇乙酸酯系溶劑;丙二醇二乙酸酯、1,3-丁二醇二乙酸酯等二乙酸酯類;乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚、二乙二醇二甲醚、二乙二醇單乙醚、二乙二醇二乙醚、丙二醇單甲醚、二丙二醇二甲醚等二醇醚系溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等非質子性醯胺溶劑;γ-丁內酯等內酯系溶劑;四氫呋喃等環狀醚系溶劑;苯、甲苯、二甲苯、萘等不飽和烴系溶劑;N-庚烷、N-己烷、N-辛烷等飽和烴系溶劑;甲苯、二甲苯等芳香族烴類等有機溶劑。於該等溶劑中,就其他成分之溶解性之方面而言,可適宜地使用二醇醚乙酸酯系溶劑、卡必醇乙酸酯系溶劑、二醇醚系溶劑、酯系溶劑。其中,作為本發明所使用之溶劑,就其他成分之溶解性或塗佈適性之方面而言,較佳為選自由丙二醇單甲醚乙酸酯、丙二醇單甲醚、丁基卡必醇乙酸酯(BCA)、乙酸3-甲氧基-3-甲基-1-丁酯、乙氧基丙酸乙酯、乳酸乙酯、及乙酸3-甲氧基丁酯所組成之群中之1種以上。 [solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the photosensitive colored resin composition and can dissolve or disperse them. A solvent can be used individually or in combination of 2 or more types. As specific examples of solvents, for example, alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; Carbitol-based solvents such as oxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate Esters, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexanol acetate and other ester solvents; acetone , methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and other ketone solvents; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3 acetic acid - Glycol ether acetate-based solvents such as methyl-1-butyl ester, 3-methoxybutyl acetate, and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethyl acetate Carbitol acetate solvents such as ethyl ethyl ester and butyl carbitol acetate (BCA); diacetate esters such as propylene glycol diacetate and 1,3-butanediol diacetate; Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether Glycol ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents; γ-butyrolactone, etc. Lactone solvents; tetrahydrofuran and other cyclic ether solvents; benzene, toluene, xylene, naphthalene and other unsaturated hydrocarbon solvents; N-heptane, N-hexane, N-octane and other saturated hydrocarbon solvents; toluene, Organic solvents such as aromatic hydrocarbons such as xylene. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents can be suitably used from the point of solubility of other components. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility of other components or coating suitability. 1 of the group consisting of ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate more than one species.
於本發明之感光性著色樹脂組合物中,溶劑之含量於能夠精度良好地形成著色層之範圍內適當設定即可。相對於含有該溶劑之感光性著色樹脂組合物之總量,通常可為55質量%~95質量%之範圍內,較佳為65質量%~88質量%之範圍內。藉由上述溶劑之含量為上述範圍內,可使其塗佈性變得優異。In the photosensitive colored resin composition of this invention, content of a solvent should just be set suitably within the range which can form a colored layer with high precision. It can exist in the range of 55 mass % - 95 mass % normally with respect to the whole quantity of the photosensitive coloring resin composition containing this solvent, Preferably it can exist in the range of 65 mass % - 88 mass %. When content of the said solvent exists in the said range, it can become excellent in applicability.
[分散劑] 於本發明之感光性著色樹脂組合物中,上述色材可藉由分散劑而分散於溶劑中使用。於本發明中,分散劑可自先前公知之分散劑中適當選擇使用。作為分散劑,例如可使用:陽離子系、陰離子系、非離子系、兩性、矽酮系、氟系等之界面活性劑。於界面活性劑中,就能夠均勻且微細地分散之方面而言,較佳為高分子分散劑。 [Dispersant] In the photosensitive colored resin composition of the present invention, the above-mentioned color material can be used by being dispersed in a solvent with a dispersant. In the present invention, the dispersant can be appropriately selected from conventionally known dispersants. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine can be used. Among the surfactants, polymer dispersants are preferred in terms of being able to disperse uniformly and finely.
作為高分子分散劑,例如可例舉:聚丙烯酸酯等不飽和羧酸酯之(共)聚合物類;聚丙烯酸等不飽和羧酸之(共)聚合物之(部分)胺鹽、(部分)銨鹽或(部分)烷基胺鹽類;含有羥基之聚丙烯酸酯等含有羥基之不飽和羧酸酯之(共)聚合物或該等之改性物;聚胺基甲酸酯類;不飽和聚醯胺類;聚矽氧烷類;長鏈聚胺基醯胺磷酸鹽類;聚伸乙基亞胺衍生物(藉由聚(低級伸烷基亞胺)與含有游離羧基之聚酯之反應所獲得之醯胺或該等之鹼);聚烯丙基胺衍生物(使聚烯丙基胺與選自具有游離之羧基之聚酯、聚醯胺或酯與醯胺之共縮合物(聚酯醯胺)之3種化合物中之1種以上化合物進行反應所獲得之反應產物)等。 於高分子分散劑為共聚物之情形時,可為嵌段共聚物、接枝共聚物或無規共聚物之任一種,就分散性之觀點而言,較佳為嵌段共聚物及接枝共聚物。 Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; ) ammonium salts or (partial) alkylamine salts; (co)polymers of hydroxyl-containing polyacrylates and other unsaturated carboxylic acid esters containing hydroxyl groups or their modified products; polyurethanes; Saturated polyamides; Polysiloxanes; Long-chain polyaminoamide phosphates; Polyethyleneimine derivatives (by poly(lower alkyleneimine) and polyesters containing free carboxyl groups Amides or bases thereof obtained by the reaction); polyallylamine derivatives (cocondensation of polyallylamine with polyesters, polyamides or esters and amides selected from the group having free carboxyl groups) A reaction product obtained by reacting one or more of the three compounds of the compound (polyesteramide), etc. When the polymer dispersant is a copolymer, it can be any of block copolymer, graft copolymer or random copolymer. From the viewpoint of dispersibility, block copolymer and graft copolymer are preferred. copolymer.
分散劑可根據色材之種類而適當選擇使用分散性良好者,並無特別限定,於使上述三芳基甲烷系染料之色澱色材分散之情形時,作為分散劑,較佳為使用作為酸性之高分子分散劑之酸性分散劑。 作為色澱色材之分散所使用之酸性分散劑,例如可適宜地使用選自下文所述之具有通式(I)所表示之結構單元之聚合物、及含有羧基之嵌段共聚物中之至少1種。 於進而使用顏料作為色材並使其分散之情形時,可根據顏料之種類,使用選自由酸性或鹼性之高分子分散劑及胺基甲酸酯系分散劑所組成之群中之至少1種,可使用酸性或鹼性之高分子分散劑。於使經鹼性處理之顏料分散之情形時,較佳為使用作為酸性之高分子分散劑之酸性分散劑,於使經酸性處理之顏料分散之情形時,較佳為使用作為鹼性之高分子分散劑之鹼性分散劑。 作為鹼性分散劑,例如可適宜地使用選自由包含具有三級胺之重複單元之聚合物、及包含具有三級胺之重複單元之聚合物中之胺基中的至少一部分與有機酸化合物形成鹽而成之鹽型聚合物所組成之群中之至少1種。 胺基甲酸酯系分散劑係於1分子內具有1個以上胺基甲酸酯鍵(-NH-COO-)之化合物。作為胺基甲酸酯系分散劑,例如可適宜地使用1分子中具有2個以上異氰酸基之聚異氰酸酯類與單末端或兩末端具有羥基之聚酯類之反應產物。 The dispersing agent can be appropriately selected according to the type of color material, and the one with good dispersibility is not particularly limited. When dispersing the color material of the above-mentioned triarylmethane dye lake, as a dispersant, it is preferable to use an acidic color material. Acidic dispersant of polymer dispersant. As the acidic dispersant used for the dispersion of the color lake color material, for example, one selected from the polymers with structural units represented by the general formula (I) described below and the block copolymers containing carboxyl groups can be suitably used. At least 1 species. When further using a pigment as a color material and dispersing it, at least one selected from the group consisting of acidic or alkaline polymer dispersants and urethane-based dispersants can be used depending on the type of pigment. Acidic or alkaline polymer dispersants can be used. In the case of dispersing an alkaline-treated pigment, it is preferable to use an acidic dispersant as an acidic polymer dispersant, and in the case of dispersing an acid-treated pigment, it is preferable to use an alkaline high Alkaline dispersant of molecular dispersant. As the basic dispersant, for example, a polymer selected from repeating units having a tertiary amine, and at least a part of the amine groups in a polymer containing a repeating unit having a tertiary amine formed with an organic acid compound can be suitably used. At least one of the group consisting of salt-type polymers formed from salts. The urethane-based dispersant is a compound having one or more urethane bonds (-NH-COO-) in one molecule. As the urethane-based dispersant, for example, a reaction product of a polyisocyanate having two or more isocyanate groups in one molecule and a polyester having a hydroxyl group at one or both ends can be suitably used.
<具有通式(I)所表示之結構單元之聚合物> 具有下述通式(I)所表示之結構單元之聚合物可較佳地用作上述三芳基甲烷系染料之色澱色材之分散劑。若使用具有下述通式(I)所表示之結構單元之聚合物作為酸性分散劑,則能夠提高上述三芳基甲烷系染料之色澱色材之分散性與耐熱性,抑制加熱後之色澱色材之色度變化。又,於併用色澱色材與顏料作為色材之情形時,藉由使用具有下述通式(I)所表示之結構單元之聚合物作為分散劑,能夠形成提高顏料之分散性及保存穩定性、基板密接性及塗膜均一性提高之著色層。 由於具有下述通式(I)所表示之結構單元之聚合物為乙烯性不飽和單體之聚合物,故而推定與聚醚系或聚酯系聚合物相比,骨架之耐熱性較高,且於該聚合物中存在複數個之酸性磷化合物基(-P(=O)(-R 12)(OH))及其鹽(-P(=O)(-R 12)(O -X +))對經微粒子化之色材之表面的吸附力較強。又,推定若成為色材表面被酸性磷化合物基及其鹽之至少一種所被覆之狀態,則可抑制過氧自由基等活性氧對色澱色材之色素骨架之攻擊(奪氫或置換反應等),而抑制色澱色材之劣化(氧化劣化)。 <Polymer having a structural unit represented by the general formula (I)> A polymer having a structural unit represented by the following general formula (I) can be preferably used as a coloring material for the above-mentioned triarylmethane-based dye lake Dispersant. If a polymer having a structural unit represented by the following general formula (I) is used as an acidic dispersant, the dispersibility and heat resistance of the color lake material of the above-mentioned triarylmethane dyes can be improved, and the color lake after heating can be suppressed. Chroma change of color material. Also, when using a color lake material and a pigment together as a color material, by using a polymer having a structural unit represented by the following general formula (I) as a dispersant, it is possible to form an improved pigment dispersibility and storage stability. Colored layer with improved performance, substrate adhesion and uniformity of coating film. Since the polymer having the structural unit represented by the following general formula (I) is a polymer of an ethylenically unsaturated monomer, it is estimated that the heat resistance of the skeleton is higher than that of a polyether or polyester polymer. And there are multiple acidic phosphorus compound groups (-P(=O)(-R 12 )(OH)) and their salts (-P(=O)(-R 12 )(O - X + )) Strong adsorption to the surface of the micronized color material. In addition, it is estimated that if the surface of the color material is covered with at least one of the acidic phosphorus compound group and its salt, the attack (hydrogen abstraction or replacement reaction) of active oxygen such as peroxyl radicals on the pigment skeleton of the color lake material can be suppressed. etc.) to suppress the deterioration of the lake material (oxidative deterioration).
[化10] (通式(I)中,L 11為直接鍵或二價連結基,R 11為氫原子或甲基,R 12為羥基、烴基、-[CH(R 13)-CH(R 14)-O] x1-R 15、-[(CH 2) y1-O] z1-R 15、或-O-R 16所表示之一價基,R 16為烴基、-[CH(R 13)-CH(R 14)-O] x1-R 15、-[(CH 2) y1-O] z1-R 15、-C(R 17)(R 18)-C(R 19)(R 20)-OH、或-CH 2-C(R 21)(R 22)-CH 2-OH所表示之一價基。 R 13及R 14分別獨立為氫原子或甲基,R 15為氫原子、烴基、-CHO、-CH 2CHO、-CO-CH=CH 2、-CO-C(CH 3)=CH 2或-CH 2COOR 23所表示之一價基,R 23為氫原子或碳數為1個以上5個以下之烷基。R 17、R 18、R 19、R 20、R 21及R 22分別獨立為氫原子、烴基、或具有選自醚鍵及酯鍵中之1種以上之烴基,R 17及R 19可互相鍵結而形成環結構。於形成上述環狀結構之情形時,該環狀結構可進而具有取代基R 24,R 24為烴基、或具有選自醚鍵及酯鍵中之1種以上之烴基。上述烴基可具有取代基。X表示氫原子或有機陽離子。x1表示1以上18以下之整數,y1表示1以上5以下之整數,z1表示1以上18以下之整數) [chemical 10] (In general formula (I), L 11 is a direct bond or a divalent linking group, R 11 is a hydrogen atom or a methyl group, R 12 is a hydroxyl group, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O ] x1 -R 15 , -[(CH 2 ) y1 -O] z1 -R 15 , or a valent group represented by -OR 16 , where R 16 is a hydrocarbon group, -[CH(R 13 )-CH(R 14 ) -O] x1 -R 15 , -[(CH 2 ) y1 -O] z1 -R 15 , -C(R 17 )(R 18 )-C(R 19 )(R 20 )-OH, or -CH 2 A valent group represented by -C(R 21 )(R 22 )-CH 2 -OH. R 13 and R 14 are independently a hydrogen atom or a methyl group, and R 15 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 A valence group represented by CHO, -CO-CH=CH 2 , -CO-C(CH 3 )=CH 2 or -CH 2 COOR 23 , R 23 is a hydrogen atom or a carbon number of 1 to 5 Alkyl. R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group having one or more selected from ether bonds and ester bonds, and R 17 and R 19 Can be bonded to each other to form a ring structure. In the case of forming the above-mentioned ring structure, the ring structure can further have a substituent R 24 , R 24 is a hydrocarbon group, or has more than one selected from ether bonds and ester bonds The above-mentioned hydrocarbon group may have a substituent. X represents a hydrogen atom or an organic cation. x1 represents an integer of 1 to 18, y1 represents an integer of 1 to 5, and z1 represents an integer of 1 to 18)
於通式(I)中,L 11為直接鍵或二價連結基。此處,L 11為直接鍵意指磷原子不經由連結基而直接鍵結於主鏈骨架之碳原子。 作為L 11中之二價連結基,只要能夠將主鏈骨架之碳原子與磷原子連結,則無特別限制。作為L 11中之二價連結基,例如可例舉:直鏈、支鏈或環狀之伸烷基;具有羥基之直鏈、支鏈或環狀之伸烷基;伸芳基、-CONH-基、-COO-基、-NHCOO-基、醚基(-O-基)、硫醚基(-S-基)、及該等之組合等。再者,於本發明中,二價連結基之鍵之朝向為任意。即,於二價連結基包含-CONH-之情形時,可為-CO為主鏈之碳原子側且-NH為側鏈之磷原子側,亦可相反地,-NH為主鏈之碳原子側且-CO為側鏈之磷原子側。 In the general formula (I), L 11 is a direct bond or a divalent linking group. Here, L 11 being a direct bond means that a phosphorus atom is directly bonded to a carbon atom of the main chain skeleton without a linking group. The divalent linking group in L 11 is not particularly limited as long as it can link a carbon atom of the main chain skeleton with a phosphorus atom. As the divalent linking group in L11 , for example, it can be exemplified: a linear, branched or cyclic alkylene group; a linear, branched or cyclic alkylene group having a hydroxyl group; an arylylene group, -CONH - group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. Furthermore, in the present invention, the orientation of the bond of the divalent linking group is arbitrary. That is, when the divalent linking group includes -CONH-, -CO may be the carbon atom side of the main chain and -NH may be the phosphorus atom side of the side chain, or conversely, -NH may be the carbon atom side of the main chain side and -CO is the phosphorus atom side of the side chain.
其中,就分散性之方面而言,通式(I)中之L 11較佳為含有-CONH-基、或-COO-基之二價連結基。 例如,於L 11為包含-COO-基之二價連結基之情形時,較佳為L 11為-COO-L 11'-基(此處,L 11'為可具有羥基之碳數為1個以上8個以下之伸烷基、-[CH(R L11)-CH(R L12)-O] x-、或-[(CH 2) y-O] z-(CH 2) y-O-、-[CH(R L13)] w-O-,R L11、R L12及R L13分別獨立為氫原子、甲基、或羥基。x表示1以上18以下之整數,y表示1以上5以下之整數,z表示1以上18以下之整數,w表示1以上18以下之整數)。 Among them, in terms of dispersibility, L 11 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group. For example, when L 11 is a divalent linking group including a -COO- group, it is preferable that L 11 is a -COO-L 11' -group (here, L 11' is a carbon number that may have a hydroxyl group and is 1 More than 8 alkylene groups, -[CH(R L11 )-CH(R L12 )-O] x -, or -[(CH 2 ) y -O] z -(CH 2 ) y -O- , -[CH(R L13 )] w -O-, R L11 , R L12 and R L13 are independently a hydrogen atom, a methyl group, or a hydroxyl group. x represents an integer ranging from 1 to 18, and y represents an integer ranging from 1 to 5 Integer, z represents an integer ranging from 1 to 18, and w represents an integer ranging from 1 to 18).
L 11'中之碳數為1個以上8個以下之伸烷基可為直鏈狀、支鏈狀、或環狀之任一種,例如為亞甲基、伸乙基、三亞甲基、伸丙基、各種伸丁基、各種伸戊基、各種伸己基、各種伸辛基等,一部分氫可被取代為羥基。 x為1以上18以下之整數,較佳為1以上4以下之整數,更佳為1以上2以下之整數,y為1以上5以下之整數,較佳為1以上4以下之整數,更佳為2或3。z為1以上18以下之整數,較佳為1以上4以下之整數,更佳為1以上2以下之整數。w為1以上18以下之整數,較佳為1以上4以下之整數。 The alkylene group with 1 to 8 carbons in L 11' can be linear, branched, or cyclic, such as methylene, ethylene, trimethylene, alkene In propyl groups, various butyl groups, various pentylene groups, various hexylene groups, various octylene groups, etc., a part of hydrogen may be substituted by hydroxyl groups. x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably for 2 or 3. z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2. w is an integer of 1 to 18, preferably an integer of 1 to 4.
作為通式(I)中之L 11之適宜之具體例,例如可例舉:-COO-CH 2CH(OH)CH 2-O-、-COO-CH 2CH 2-O-CH 2CH(OH)CH 2-O-、-COO-CH 2C(CH 2CH 3)(CH 2OH)CH 2-O-等,但不限定於該等。 As a suitable specific example of L 11 in the general formula (I), for example, -COO-CH 2 CH(OH)CH 2 -O-, -COO-CH 2 CH 2 -O-CH 2 CH( OH)CH 2 -O-, -COO-CH 2 C(CH 2 CH 3 )(CH 2 OH)CH 2 -O-, etc., but not limited thereto.
作為R 12中之烴基,例如可例舉碳數為1個以上18個以下之烷基、碳數為2個以上18個以下之烯基、芳烷基、及芳基等。 上述碳數為1個以上18個以下之烷基可為直鏈狀、支鏈狀、環狀之任一種,例如可例舉:甲基、乙基、正丙基、異丙基、正丁基、環戊基、環己基、𦯉基、異𦯉基、雙環戊基、金剛烷基、低級烷基取代金剛烷基等。 上述碳數為2個以上18個以下之烯基可為直鏈狀、支鏈狀、環狀之任一種。作為此種烯基,例如可例舉:乙烯基、烯丙基、丙烯基等。烯基之雙鍵之位置並無限定,就所獲得之聚合物之反應性之方面而言,較佳為雙鍵處於烯基之末端。 作為芳基,可例舉:苯基、聯苯基、萘基、甲苯基、二甲苯基等,可進而具有取代基。芳基之碳數較佳為6個以上24個以下,進而較佳為6個以上12個以下。 又,作為芳烷基,可例舉:苄基、苯乙基、萘基甲基、聯苯基甲基等,可進而具有取代基。芳烷基之碳數較佳為7個以上20個以下,進而較佳為7個以上14個以下。 上述烷基或烯基可具有取代基,作為該取代基,可例舉:F、Cl、Br等鹵素原子、硝基等。 又,作為上述芳基或芳烷基等之芳香環之取代基,除了碳數為1個以上4個以下之直鏈狀、支鏈狀之烷基以外,可例舉:烯基、硝基、鹵素原子等。 再者,上述較佳之碳數中不包括取代基之碳數。 於上述R 12中,x1與上述x相同,y1與上述y相同,z1與上述z相同。 作為R 15~R 22中之烴基,例如可例舉與上述R 12中之烴基相同者。 As the hydrocarbon group in R12 , for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, and an aryl group may be mentioned. The above-mentioned alkyl group having 1 to 18 carbons may be linear, branched, or cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl Base, cyclopentyl, cyclohexyl, ??, iso??, dicyclopentyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. As such an alkenyl group, a vinyl group, an allyl group, a propenyl group etc. are mentioned, for example. The position of the double bond of the alkenyl group is not limited, but the double bond is preferably located at the end of the alkenyl group in terms of the reactivity of the obtained polymer. As an aryl group, a phenyl group, a biphenylyl group, a naphthyl group, a tolyl group, a xylyl group etc. are mentioned, It may further have a substituent. The carbon number of the aryl group is preferably from 6 to 24, and more preferably from 6 to 12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group etc. are mentioned, It may further have a substituent. The number of carbon atoms in the aralkyl group is preferably from 7 to 20, and more preferably from 7 to 14. The above-mentioned alkyl group or alkenyl group may have a substituent, and the substituent may, for example, be a halogen atom such as F, Cl or Br, or a nitro group. In addition, as the substituent of the aromatic ring such as the above-mentioned aryl group or aralkyl group, in addition to straight-chain or branched-chain alkyl groups having 1 to 4 carbon atoms, alkenyl groups, nitro groups, etc. , halogen atoms, etc. Furthermore, the carbon number of the substituent is not included in the above preferred carbon number. In the above-mentioned R12 , x1 is the same as the above-mentioned x, y1 is the same as the above-mentioned y, and z1 is the same as the above-mentioned z. Examples of the hydrocarbon group in R 15 to R 22 include the same ones as those in R 12 described above.
R 17、R 18、R 19、R 20、R 21及R 22中之具有選自醚鍵及酯鍵中之1種以上之烴基為-R'-O-R"、-R'-(C=O)-O-R"、或-R'-O-(C=O)-R"(R'及R"為烴基、或藉由醚鍵及酯鍵之至少一者鍵結有烴基之基)所表示之基。可於1個基中具有2個以上醚鍵及酯鍵。作為烴基為一價之情形,可例舉:烷基、烯基、芳烷基、芳基,作為烴基為二價之情形,可例舉:伸烷基、伸烯基、伸芳基、及該等之組合基。 R 17 , R 18 , R 19 , R 20 , R 21 and R 22 have at least one hydrocarbon group selected from ether bonds and ester bonds as -R'-OR", -R'-(C=O )-OR", or -R'-O-(C=O)-R"(R' and R" are hydrocarbon groups, or groups that are bonded to hydrocarbon groups through at least one of ether bonds and ester bonds) foundation. One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, examples include alkyl, alkenyl, aralkyl, and aryl groups. When the hydrocarbon group is divalent, examples include alkylene, alkenylene, arylylene, and the combined basis of such.
於R 17與R 19鍵結而形成環結構之情形時,形成環結構之碳數較佳為5個以上8個以下,更佳為6、即為6員環,較佳為形成環己烷環。 取代基R 24中之烴基、或具有選自醚鍵及酯鍵中之1種以上之烴基可設為與上述R 17、R 18、R 19、R 20、R 21及R 22中相同者。 When R 17 and R 19 are bonded to form a ring structure, the number of carbons forming the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, preferably cyclohexane ring. The hydrocarbon group in the substituent R 24 , or the hydrocarbon group having one or more types selected from ether linkages and ester linkages may be the same as those of the aforementioned R 17 , R 18 , R 19 , R 20 , R 21 and R 22 .
就所分散之粒子之分散性及分散穩定性優異之方面而言,上述R 12較佳為羥基、烴基、-[CH(R 13)-CH(R 14)-O] x1-R 15、-[(CH 2) y1-O] z1-R 15、或-O-R 16所表示之一價基,更佳為羥基、甲基、乙基、乙烯基、可具有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(R 13)-CH(R 14)-O] x1-R 15、-[(CH 2) y1-O] z1-R 15、或-O-R 16所表示之一價基且R 13及R 14分別獨立為氫原子或甲基、R 15為-CO-CH=CH 2或-CO-C(CH 3)=CH 2者,其中,R 12更佳為可具有取代基之芳基、乙烯基、甲基及羥基。 In terms of excellent dispersibility and dispersion stability of the dispersed particles, the above-mentioned R 12 is preferably a hydroxyl group, a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , - [(CH 2 ) y1 -O] z1 -R 15 , or a valent group represented by -OR 16 , more preferably hydroxyl, methyl, ethyl, vinyl, aryl or aralkyl that may have substituents , vinyl, allyl, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , -[(CH 2 ) y1 -O] z1 -R 15 , or -OR 16 One valent group and R 13 and R 14 are independently a hydrogen atom or a methyl group, R 15 is -CO-CH=CH 2 or -CO-C(CH 3 )=CH 2 , wherein, R 12 is more preferably Aryl group, vinyl group, methyl group and hydroxyl group which may have a substituent.
又,就提高耐鹼性之方面而言,R 12較佳為烴基、-[CH(R 13)-CH(R 14)-O] x1-R 15、或-[(CH 2) y1-O] z1-R 15所表示之一價基。於具有碳原子直接鍵結於磷原子之結構之情形時,推定由於難以水解,故而能夠形成耐鹼性優異之樹脂層。其中,就耐鹼性優異、且所分散之粒子之分散性及分散穩定性優異之方面而言,R 12較佳為甲基、乙基、可具有取代基之芳基或芳烷基、乙烯基、烯丙基、-[CH(R 13)-CH(R 14)-O] x1-R 15、或-[(CH 2) y1-O] z1-R 15所表示之一價基且R 13及R 14分別獨立為氫原子或甲基、R 15為-CO-CH=CH 2或-CO-C(CH 3)=CH 2者。其中,就分散性之方面而言,R 12更佳為可具有取代基之芳基。 Also, in terms of improving alkali resistance, R 12 is preferably a hydrocarbon group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH 2 ) y1 -O ] z1 -R 15 represents a valence group. In the case of having a structure in which carbon atoms are directly bonded to phosphorus atoms, it is presumed that since hydrolysis is difficult, a resin layer excellent in alkali resistance can be formed. Among them, R12 is preferably a methyl group, an ethyl group, an aryl group or an aralkyl group that may have a substituent, vinyl group, allyl group, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH 2 ) y1 -O] z1 -R 15 represents a valent group and R 13 and R 14 are each independently a hydrogen atom or a methyl group, and R 15 is -CO-CH=CH 2 or -CO-C(CH 3 )=CH 2 . Among them, in terms of dispersibility, R 12 is more preferably an aryl group which may have a substituent.
又,於通式(I)中,X表示氫原子或有機陽離子。有機陽離子係指陽離子部分包含碳原子者。作為有機陽離子,例如可例舉:咪唑鎓陽離子、吡啶鎓陽離子、脒鎓陽離子、哌啶鎓陽離子、吡咯啶鎓陽離子、四烷基銨陽離子及三烷基銨陽離子等銨陽離子、三烷基鋶陽離子等鋶陽離子、四烷基鏻陽離子等鏻陽離子等。其中,就分散性與鹼性顯影性之方面而言,較佳為經質子化之含氮有機陽離子。 其中,於有機陽離子具有乙烯性不飽和鍵之情形時,就能夠賦予硬化性之方面而言較佳。 Also, in the general formula (I), X represents a hydrogen atom or an organic cation. Organic cations refer to those in which the cation portion contains carbon atoms. Examples of organic cations include ammonium cations such as imidazolium cations, pyridinium cations, amidinium cations, piperidinium cations, pyrrolidinium cations, tetraalkylammonium cations, and trialkylammonium cations, and trialkylammonium cations. cations such as cerium cations, phosphonium cations such as tetraalkylphosphonium cations, and the like. Among them, protonated nitrogen-containing organic cations are preferred in terms of dispersibility and alkali developability. Among them, when the organic cation has an ethylenically unsaturated bond, it is preferable in terms of being able to impart curability.
通式(I)所表示之結構單元可於聚合物中單獨包含1種,亦可包含2種以上。The structural unit represented by general formula (I) may be contained in a polymer individually by 1 type, and may contain 2 or more types.
於聚合物中,通式(I)所表示之結構單元中,可包含X為氫原子之結構單元與X為有機陽離子之結構單元之兩種結構單元。於包含該兩種結構單元之情形時,只要發揮良好之分散性、及分散穩定性即可,並無特別限制,X為有機陽離子之結構單元數之比例相對於通式(I)所表示之結構單元之合計之結構單元數,較佳為0以上50莫耳%以下。In the polymer, the structural unit represented by the general formula (I) may contain two structural units in which X is a hydrogen atom and X is a structural unit of an organic cation. In the case of including the two structural units, as long as good dispersibility and dispersion stability can be exerted, there is no special limitation, and X is the ratio of the number of structural units of organic cations to that represented by the general formula (I). The total number of structural units of the structural units is preferably from 0 to 50 mol%.
具有通式(I)所表示之結構單元之聚合物之合成方法並無特別限定,例如可參照日本專利特開2017-2191號公報合成具有通式(I)所表示之結構單元之聚合物。具有通式(I)所表示之結構單元之聚合物較佳為側鏈具有環氧基及環狀醚基之至少一者之聚合物與酸性磷化合物之反應產物,且為酸性磷化合物基之至少一部分可形成鹽之聚合物。The synthesis method of the polymer having the structural unit represented by the general formula (I) is not particularly limited. For example, a polymer having the structural unit represented by the general formula (I) can be synthesized with reference to Japanese Patent Application Laid-Open No. 2017-2191. The polymer having the structural unit represented by the general formula (I) is preferably the reaction product of a polymer having at least one of epoxy group and cyclic ether group in the side chain and an acidic phosphorus compound, and is a compound of the acidic phosphorus compound group. At least a portion of the polymer is capable of forming a salt.
於本發明之實施方式中,具有通式(I)所表示之結構單元之聚合物就分散性之方面而言,較佳為進而具有溶劑親和性部位。作為此種聚合物,其中,就分散性、及保存穩定性優異,長期保管後亦能夠形成高對比度之塗膜之方面而言,較佳為具有上述通式(I)所表示之結構單元與下述通式(II)所表示之結構單元之接枝共聚物,或具有上述通式(I)所表示之結構單元與下述通式(III)所表示之結構單元之嵌段共聚物。In an embodiment of the present invention, it is preferable that the polymer having the structural unit represented by the general formula (I) further has a solvent-affinity site from the viewpoint of dispersibility. Such a polymer preferably has a structural unit represented by the above-mentioned general formula (I) and A graft copolymer of a structural unit represented by the following general formula (II), or a block copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the following general formula (III).
[化11] (通式(II)中,L 21表示直接鍵或二價連結基,R 25表示氫原子或甲基,Polymer表示具有下述通式(IV)所表示之結構單元之聚合物鏈。 通式(III)中,R 26為氫原子或甲基,R 27為烴基、-[CH(R 28)-CH(R 29)-O] x2-R 30、-[(CH 2) y2-O] z2-R 30、-[CO-(CH 2) y2-O] z2-R 30、-CO-O-R 30'或-O-CO-R 30"所表示之一價基,R 28及R 29分別獨立為氫原子或甲基,R 30為氫原子、烴基、-CHO、-CH 2CHO或-CH 2COOR 31所表示之一價基,R 30'為烴基、-[CH(R 28)-CH(R 29)-O] x2'-R 30、-[(CH 2) y2'-O] z2'-R 30、-[CO-(CH 2) y2'-O] z2'-R 30所表示之一價基,R 30"為碳數為1個以上18個以下之烷基,R 31為氫原子或碳數為1個以上5個以下之烷基。上述烴基可具有取代基。 x2及x2'表示1以上18以下之整數,y2及y2'表示1以上5以下之整數,z2及z2'表示1以上18以下之整數) [chemical 11] (In the general formula (II), L21 represents a direct bond or a divalent linking group, R25 represents a hydrogen atom or a methyl group, and Polymer represents a polymer chain having a structural unit represented by the following general formula (IV). In (III), R 26 is a hydrogen atom or a methyl group, R 27 is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 , -[(CH 2 ) y2 -O] z2 -R 30 , -[CO-(CH 2 ) y2 -O] z2 -R 30 , -CO-OR 30' or -O-CO-R 30" , R 28 and R 29 respectively is independently a hydrogen atom or a methyl group, R 30 is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 31 , R 30' is a hydrocarbon group, -[CH(R 28 )- CH(R 29 )-O] x2' -R 30 , -[(CH 2 ) y2' -O] z2' -R 30 , -[CO-(CH 2 ) y2' -O] z2' -R 30 Represents a valent group, R 30" is an alkyl group with 1 to 18 carbons, R 31 is a hydrogen atom or an alkyl group with 1 to 5 carbons. The above hydrocarbon groups may have substituents. x2 and x2' represent integers ranging from 1 to 18, y2 and y2' represent integers ranging from 1 to 5, z2 and z2' represent integers ranging from 1 to 18)
[化12] (通式(IV)中,R 32為氫原子或甲基,R 33為烴基、-[CH(R 34)-CH(R 35)-O] x3-R 36、-[(CH 2) y3-O] z3-R 36、-[CO-(CH 2) y3-O] z3-R 36、-CO-O-R 37或-O-CO-R 38所表示之一價基,R 34及R 35分別獨立為氫原子或甲基,R 36為氫原子、烴基、-CHO、-CH 2CHO或-CH 2COOR 39所表示之一價基,R 37為烴基、-[CH(R 34)-CH(R 35)-O] x4-R 36、-[(CH 2) y4-O] z4-R 36、-[CO-(CH 2) y4-O] z4-R 36所表示之一價基,R 38為碳數為1個以上18個以下之烷基,R 39為氫原子或碳數為1個以上5個以下之烷基,上述烴基可具有取代基。 n表示5以上200以下之整數。x3及x4表示1以上18以下之整數,y3及y4表示1以上5以下之整數,z3及z4表示1以上18以下之整數) [chemical 12] (In general formula (IV), R 32 is a hydrogen atom or a methyl group, R 33 is a hydrocarbon group, -[CH(R 34 )-CH(R 35 )-O] x3 -R 36 , -[(CH 2 ) y3 -O] z3 -R 36 , -[CO-(CH 2 ) y3 -O] z3 -R 36 , -CO-OR 37 or -O-CO-R 38 represents a valent group, R 34 and R 35 are independently a hydrogen atom or a methyl group, R 36 is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 39 , R 37 is a hydrocarbon group, -[CH(R 34 )- One of the valent groups represented by CH(R 35 )-O] x4 -R 36 , -[(CH 2 ) y4 -O] z4 -R 36 , -[CO-(CH 2 ) y4 -O] z4 -R 36 , R 38 is an alkyl group with 1 to 18 carbons, R 39 is a hydrogen atom or an alkyl group with 1 to 5 carbons, and the above hydrocarbon groups may have substituents. n represents 5 to 200 Integer. x3 and x4 represent integers ranging from 1 to 18, y3 and y4 represent integers ranging from 1 to 5, z3 and z4 represent integers ranging from 1 to 18)
(接枝共聚物) 作為酸性分散劑而較佳之接枝共聚物例如可例舉具有上述通式(I)所表示之結構單元與上述通式(II)所表示之結構單元之接枝共聚物。 於上述通式(II)中,L 21為直接鍵或二價連結基。作為L 21中之二價連結基,只要能夠將源自乙烯性不飽和鍵之碳原子與聚合物鏈連結,則並無特別限制。作為L 21中之二價連結基,例如可例舉與上述L 11中之二價連結基相同者。 (Graft Copolymer) A graft copolymer preferably used as an acidic dispersant includes, for example, a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the above general formula (II) . In the above general formula (II), L 21 is a direct bond or a divalent linking group. The divalent linking group in L21 is not particularly limited as long as it can link a carbon atom derived from an ethylenically unsaturated bond to a polymer chain. As the divalent linking group in L21 , for example, the same ones as the divalent linking group in L11 above can be mentioned.
於上述通式(II)中,Polymer表示具有上述通式(IV)所表示之結構單元之聚合物鏈。 於通式(IV)中,作為R 33中之烴基,較佳為碳數為1個以上18個以下之烷基、碳數為2個以上18個以下之烯基、芳烷基、或芳基。該等例如可例舉與上述R 12相同者。 In the above general formula (II), Polymer represents a polymer chain having a structural unit represented by the above general formula (IV). In the general formula (IV), the hydrocarbon group in R33 is preferably an alkyl group with 1 to 18 carbons, an alkenyl group with 2 to 18 carbons, an aralkyl group, or an aryl group. base. These are, for example, the same ones as those described above for R12 .
R 36較佳為氫原子、或碳數為1個以上18個以下之烷基、芳烷基、芳基、-CHO、-CH 2CHO或-CH 2COOR 39所表示之一價基,R 37較佳為碳數為1個以上18個以下之烷基、芳烷基、芳基、-[CH(R 34)-CH(R 35)-O] x4-R 36、-[(CH 2) y4-O] z4-R 36、-[CO-(CH 2) y4-O] z4-R 36所表示之一價基。R 38為碳數為1個以上18個以下之烷基,R 39表示氫原子或碳數為1個以上5個以下之烷基。 上述R 36及R 37中之碳數為1個以上18個以下之烷基、芳烷基、芳基可例舉與上述R 12相同者。 上述R 38及R 39中之烷基可例舉與上述R 12相同者。 於上述R 36、R 37及R 39為具有芳香環之基之情形時,該芳香環可進而具有取代基。作為該取代基,例如除了碳數為1個以上5個以下之直鏈狀、支鏈狀、環狀之烷基以外,可例舉:烯基、硝基、F、Cl、Br等鹵素原子等。 再者,上述較佳之碳數中不包括取代基之碳數。 於上述R 33及R 37中,x3及x4與上述x相同,y3及y4與上述y相同,z3及z4與上述z相同。 R 36 is preferably a hydrogen atom, or an alkyl group, aralkyl group, aryl group, -CHO, -CH 2 CHO or -CH 2 COOR 39 with a carbon number of 1 to 18. 37 is preferably an alkyl group, an aralkyl group, an aryl group, -[CH(R 34 )-CH(R 35 )-O] x4 -R 36 , -[(CH 2 ) y4 -O] z4 -R 36 , -[CO-(CH 2 ) y4 -O] z4 -R 36 represents a valent group. R 38 is an alkyl group with 1 to 18 carbons, and R 39 represents a hydrogen atom or an alkyl group with 1 to 5 carbons. Examples of the alkyl, aralkyl, and aryl groups having 1 to 18 carbon atoms in R 36 and R 37 above are the same as those for R 12 above. The alkyl group in R 38 and R 39 above can be exemplified by the same ones as R 12 above. When the aforementioned R 36 , R 37 and R 39 are groups having an aromatic ring, the aromatic ring may further have a substituent. Examples of such substituents include linear, branched, and cyclic alkyl groups having 1 to 5 carbon atoms, halogen atoms such as alkenyl groups, nitro groups, F, Cl, and Br, etc. wait. Furthermore, the carbon number of the substituent is not included in the above preferred carbon number. In the above-mentioned R33 and R37 , x3 and x4 are the same as the above-mentioned x, y3 and y4 are the same as the above-mentioned y, and z3 and z4 are the same as the above-mentioned z.
進而,上述R 33、R 36、R 37、R 38及R 39於不妨礙上述接枝共聚物之分散性能等之範圍內,可進而經烷氧基、羥基、羧基、胺基、環氧基、異氰酸基、氫鍵形成基等取代基所取代。又,可於合成具有該等取代基之接枝共聚物後,使其與具有與該取代基進行反應之官能基及聚合性基之化合物進行反應,而加成聚合性基。例如,可使具有羧基之接枝共聚物與(甲基)丙烯酸縮水甘油酯進行反應,或使具有異氰酸基之接枝共聚物與(甲基)丙烯酸羥乙酯進行反應,而加成聚合性基。 Furthermore, the above-mentioned R 33 , R 36 , R 37 , R 38 and R 39 may be further modified by an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, etc. within the range that does not hinder the dispersion performance of the above-mentioned graft copolymer. , isocyanate group, hydrogen bond forming group and other substituents. Moreover, after synthesizing the graft copolymer which has these substituents, it can react with the compound which has the functional group which reacts with this substituent, and a polymeric group, and can add a polymeric group. For example, a graft copolymer having a carboxyl group can be reacted with glycidyl (meth)acrylate, or a graft copolymer having an isocyanate group can be reacted with hydroxyethyl (meth)acrylate, and the addition polymeric base.
具有通式(IV)所表示之結構單元之聚合物鏈於上述結構單元中,較佳為具有源自下述物質之之結構單元:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸異𦯉基酯、(甲基)丙烯酸雙環戊酯、(甲基)丙烯酸金剛烷基酯、苯乙烯、α-甲基苯乙烯、乙烯基環己烷等。然而,並不限定於該等。Among the above-mentioned structural units, the polymer chain having a structural unit represented by general formula (IV) preferably has a structural unit derived from the following substances: methyl (meth)acrylate, ethyl (meth)acrylate , Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-Ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, iso-(meth)acrylate, (meth)acrylate base) dicyclopentyl acrylate, adamantyl (meth)acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, it is not limited to these.
於本發明之實施方式中,作為上述R 33及R 37,其中較佳為使用與下文所述之有機溶劑之溶解性優異者,根據色材分散液所使用之有機溶劑適當選擇即可。具體而言,例如於上述有機溶劑使用通常作為色材分散液之有機溶劑所使用之醚醇乙酸酯系、醚系、酯系等有機溶劑之情形時,較佳為甲基、乙基、異丁基、正丁基、2-乙基己基、2-乙氧基乙基、環己基、苄基等。 此處,以上述方式設定上述R 33及R 37之理由在於:包含上述R 33及R 37之結構單元對上述有機溶劑具有溶解性,上述單體之酸性磷化合物基及其鹽之部位對色材等粒子具有較高之吸附性,藉此能夠使色材等粒子之分散性、及穩定性特別優異。 In the embodiment of the present invention, as the above-mentioned R 33 and R 37 , those having excellent solubility with the organic solvent described below are preferably used, and may be appropriately selected according to the organic solvent used for the color material dispersion. Specifically, for example, when the above-mentioned organic solvent is used as an organic solvent such as ether alcohol acetate, ether, and ester, which are generally used as organic solvents for color material dispersions, methyl, ethyl, Isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. Here, the reason for setting the above-mentioned R33 and R37 in the above-mentioned manner is that: the structural unit including the above-mentioned R33 and R37 has solubility in the above-mentioned organic solvent, and the acidic phosphorus compound group of the above-mentioned monomer and the position of the salt thereof are color-sensitive. Particles such as color materials have high adsorption, so that the dispersibility and stability of particles such as color materials can be particularly excellent.
Polymer中之聚合物鏈之重量平均分子量較佳為500以上15000以下之範圍內,更佳為1000以上8000以下之範圍內。藉由為上述範圍,能夠保持作為分散劑之充分之立體排斥效應,並且亦能夠抑制立體效應之色材等粒子所致之分散所需之時間之增大。The weight average molecular weight of the polymer chains in the polymer is preferably in the range of 500 to 15,000, more preferably in the range of 1,000 to 8,000. By being in the above-mentioned range, sufficient steric repulsion effect as a dispersant can be maintained, and an increase in the time required for dispersion by particles such as a color material having a steric effect can also be suppressed.
又,作為標準,較佳為Polymer中之聚合物鏈相對於組合使用之有機溶劑,23℃下之溶解度為50(g/100 g溶劑)以上。Also, as a standard, it is preferable that the polymer chain in the polymer has a solubility of 50 (g/100 g solvent) or more at 23° C. with respect to the organic solvent used in combination.
上述聚合物鏈可為均聚物,亦可為共聚物。又,通式(II)所表示之結構單元所含之聚合物鏈於接枝共聚物中,可為單獨1種,亦可混合2種以上。The aforementioned polymer chains may be homopolymers or copolymers. In addition, the polymer chains contained in the structural unit represented by the general formula (II) may be one type alone or two or more types may be mixed in the graft copolymer.
相對於上述接枝共聚物之全部結構單元,上述通式(I)所表示之結構單元較佳為以其合計為3質量%以上80質量%以下之比例含有,更佳為10質量%以上70質量%以下,進而較佳為20質量%以上60質量%以下。若接枝共聚物中之通式(I)所表示之結構單元之合計含量處於上述範圍內,則與接枝共聚物中之粒子之親和性部位之比例變得合適,且能夠抑制針對有機溶劑之溶解性之降低,因此對色材等粒子之吸附性變得良好,可獲得優異之分散性、及分散穩定性。又,上述接枝共聚物之酸性磷化合物基能夠穩定地局部存在於色材周邊,因此可獲得耐熱性或對比度優異之彩色濾光片。 另一方面,相對於上述接枝共聚物之全部結構單元,上述通式(II)所表示之結構單元較佳為以20質量%以上97質量%以下之比例含有,更佳為25質量%以上95質量%以下,進而較佳為40質量%以上90質量%以下。 再者,於本發明中,共聚物中之各結構單元之含有比例係根據合成共聚物時之添加量所算出。 The structural unit represented by the above-mentioned general formula (I) is preferably contained in a ratio of 3% by mass to 80% by mass in total, more preferably 10% by mass to 70% by mass, relative to all the structural units of the above-mentioned graft copolymer. % by mass or less, more preferably not less than 20% by mass and not more than 60% by mass. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity sites to the particles in the graft copolymer becomes appropriate, and the reaction to the organic solvent can be suppressed. The solubility of the product is reduced, so the adsorption of particles such as color materials becomes better, and excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the above-mentioned graft copolymer can stably exist locally around the color material, so a color filter excellent in heat resistance or contrast can be obtained. On the other hand, the structural unit represented by the above-mentioned general formula (II) is preferably contained in a ratio of 20% by mass to 97% by mass, more preferably 25% by mass or more, with respect to all the structural units of the above-mentioned graft copolymer 95% by mass or less, more preferably 40% by mass or more and 90% by mass or less. In addition, in this invention, the content ratio of each structural unit in a copolymer is calculated from the addition amount at the time of synthesizing a copolymer.
又,上述接枝共聚物之重量平均分子量較佳為1000以上500000以下之範圍內,更佳為3000以上400000以下之範圍內,進而較佳為5000以上300000以下之範圍內。藉由為上述範圍,而能夠使色材等粒子均勻地分散。In addition, the weight average molecular weight of the graft copolymer is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 400,000, and still more preferably in the range of 5,000 to 300,000. Particles, such as a coloring material, can be uniformly disperse|distributed by being the said range.
本發明之實施方式所使用之上述接枝共聚物除了上述通式(I)所表示之結構單元及上述通式(II)所表示之結構單元以外,可進而具有其他結構單元。例如可適當選擇能夠與衍生上述通式(I)所表示之結構單元之乙烯性不飽和單體等共聚之乙烯性不飽和單體進行共聚,而導入其他結構單元。The graft copolymer used in the embodiment of the present invention may further have other structural units in addition to the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II). For example, an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer derived from the structural unit represented by the general formula (I) can be appropriately selected and copolymerized to introduce another structural unit.
(嵌段共聚物) 作為酸性分散劑而較佳之嵌段共聚物例如可例舉具有包含上述通式(I)所表示之結構單元之嵌段部與包含上述通式(III)所表示之結構單元之嵌段部的嵌段共聚物。 於該嵌段共聚物中,於包含上述通式(I)所表示之結構單元之嵌段部中,上述通式(I)所表示之結構單元較佳為合計包含3個以上。其中,就使分散性變得良好、提高耐熱性之方面而言,較佳為包含3個以上200個以下,更佳為包含3個以上50個以下,進而更佳為包含3個以上30個以下。 上述通式(I)所表示之結構單元作為色材親和性部位發揮功能即可,可包含1種,亦可包含2種以上結構單元。於包含2種以上結構單元之情形時,於包含上述通式(I)所表示之結構單元之嵌段部內,2種以上結構單元可隨機排列。 (block copolymer) A preferred block copolymer as an acidic dispersant includes, for example, one having a block portion containing a structural unit represented by the above general formula (I) and a block portion containing a structural unit represented by the above general formula (III). block copolymers. In this block copolymer, in the block part containing the structural unit represented by the said general formula (I), it is preferable to contain 3 or more structural units represented by the said general formula (I) in total. Among them, in terms of improving dispersibility and improving heat resistance, it is preferable to include 3 or more and 200 or less, more preferably include 3 or more and 50 or less, and still more preferably include 3 or more and 30 or less. the following. The structural unit represented by the above-mentioned general formula (I) only needs to function as a color material affinity site, and may contain one type, or may contain two or more types of structural units. In the case of including two or more structural units, two or more structural units may be randomly arranged in the block portion containing the structural unit represented by the above general formula (I).
於上述嵌段共聚物中,上述通式(I)所表示之結構單元之合計之含有比例相對於上述嵌段共聚物之全部結構單元,較佳為5質量%以上80質量%以下,更佳為10質量%以上70質量%以下,進而較佳為20質量%以上60質量%以下。 若處於上述範圍內,則與嵌段共聚物中之粒子之親和性部位之比例變得合適,且能夠抑制針對有機溶劑之溶解性之降低,因此對色材等粒子之吸附性變得良好,可獲得優異之分散性、及分散穩定性。又,上述嵌段共聚物之酸性磷化合物基能夠穩定地存在於色材周邊,因此可獲得耐熱性或對比度優異之彩色濾光片。 In the above-mentioned block copolymer, the total content ratio of the structural units represented by the above-mentioned general formula (I) is preferably 5% by mass or more and 80% by mass or less with respect to all the structural units of the above-mentioned block copolymer, more preferably It is 10 mass % or more and 70 mass % or less, More preferably, it is 20 mass % or more and 60 mass % or less. If it is within the above range, the ratio of the affinity site to the particles in the block copolymer becomes appropriate, and the decrease in solubility to organic solvents can be suppressed, so the adsorption to particles such as coloring materials becomes good, Excellent dispersibility and dispersion stability can be obtained. In addition, the acidic phosphorus compound group of the above-mentioned block copolymer can stably exist around the color material, so a color filter excellent in heat resistance or contrast can be obtained.
上述嵌段共聚物具有包含上述通式(III)所表示之結構單元之嵌段部,藉此使溶劑親和性變得良好,色材之分散性及分散穩定性良好,且耐熱性亦良好,進而對N-甲基吡咯啶酮(NMP)之耐性(耐NMP性)變得優異。The above-mentioned block copolymer has a block part including the structural unit represented by the above-mentioned general formula (III), thereby making the solvent affinity become good, the dispersibility and dispersion stability of the color material are good, and the heat resistance is also good, Furthermore, the resistance to N-methylpyrrolidone (NMP) (NMP resistance) becomes excellent.
於通式(III)中,R 27為烴基、-[CH(R 28)-CH(R 29)-O] x2-R 30、-[(CH 2) y2-O] z2-R 30、-[CO-(CH 2) y2-O] z2-R 30、-CO-O-R 30'或-O-CO-R 30"所表示之一價基。 作為R 27中之烴基,可設為與上述R 12所表示者相同。 In the general formula (III), R 27 is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 , -[(CH 2 ) y2 -O] z2 -R 30 , - [CO-(CH 2 ) y2 -O] z2 -R 30 , -CO-OR 30' or -O-CO-R 30" represents a valence group. The hydrocarbon group in R 27 can be the same as the above The one represented by R12 is the same.
又,上述R 30為氫原子、烴基、-CHO、-CH 2CHO或-CH 2COOR 31所表示之一價基,R 30'為烴基、-[CH(R 28)-CH(R 29)-O] x2'-R 30、-[(CH 2) y2'-O] z2'-R 30、-[CO-(CH 2) y2'-O] z2'-R 30所表示之一價基,R 30"為碳數為1個以上18個以下之烷基,R 31為氫原子或碳數為1個以上5個以下之烷基,上述烴基可具有取代基。 上述R 30中之烴基可設為與上述R 12所表示者相同。 於上述R 27及R 30'中,x2及x2'與上述x相同,y2及y2'與上述y相同,z2及z2'與上述z相同。 又,上述通式(III)所表示之結構單元中之R 27可互相相同,亦可不同。 In addition, the above-mentioned R 30 is a valent group represented by a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or -CH 2 COOR 31 , and R 30' is a hydrocarbon group, -[CH(R 28 )-CH(R 29 ) -O] x2' -R 30 , -[(CH 2 ) y2' -O] z2' -R 30 , -[CO-(CH 2 ) y2' -O] z2' -R 30 represents one of the valence groups , R 30" is an alkyl group with 1 to 18 carbons, R 31 is a hydrogen atom or an alkyl group with 1 to 5 carbons, and the above hydrocarbon group may have a substituent. The hydrocarbon group in the above R 30 It can be set to be the same as that represented by the above-mentioned R 12. In the above-mentioned R 27 and R 30' , x2 and x2' are the same as the above-mentioned x, y2 and y2' are the same as the above-mentioned y, and z2 and z2' are the same as the above-mentioned z. , R 27 in the structural unit represented by the above general formula (III) may be the same as or different from each other.
作為上述R 27及R 30',其中較佳為使用與下文所述之溶劑之溶解性優異者,例如可例舉與上述R 33及R 37相同者。 又,上述通式(IV)中之R 27、R 30、R 30'、R 30"及R 31於不妨礙上述嵌段共聚物之分散性能等之範圍內,可經烷氧基、羥基、羧基、胺基、環氧基、異氰酸基、氫鍵形成基等取代基所取代,又,亦可於合成上述嵌段共聚物後,使其與具有上述取代基之化合物進行反應,而加成上述取代基。又,可於合成具有該等取代基之嵌段共聚物後,使其與具有與該取代基進行反應之官能基及聚合性基之化合物進行反應,而加成聚合性基。例如,可使具有縮水甘油基之嵌段共聚物與(甲基)丙烯酸進行反應,或使具有異氰酸基之嵌段共聚物與(甲基)丙烯酸羥乙酯進行反應,而加成聚合性基。 Among them, R 27 and R 30' are preferably those having excellent solubility in the solvents described below, for example, the same ones as R 33 and R 37 above are mentioned. In addition, R 27 , R 30 , R 30' , R 30" and R 31 in the above-mentioned general formula (IV) may be modified by alkoxy, hydroxyl, Substituents such as carboxyl, amine, epoxy, isocyanate, and hydrogen bond forming groups can also be used to react with compounds having the above-mentioned substituents after synthesizing the above-mentioned block copolymers, and Add the above-mentioned substituents. Also, after synthesizing the block copolymer with these substituents, it can be reacted with a compound having a functional group and a polymerizable group that reacts with the substituent to add polymerizable For example, a block copolymer having a glycidyl group can be reacted with (meth)acrylic acid, or a block copolymer having an isocyanate group can be reacted with hydroxyethyl acrylate to add into a polymeric base.
構成包含通式(III)所表示之結構單元之嵌段部的結構單元之數並無特別限定,就溶劑親和性部位與色材親和性部位有效地發揮作用,提高色材分散液之分散性之方面而言,較佳為10以上200以下,更佳為20以上100以下,進而更佳為30以上80以下。The number of structural units constituting the block portion including the structural unit represented by the general formula (III) is not particularly limited, and the solvent-affinity site and the color material-affinity site effectively function to improve the dispersibility of the color material dispersion On the other hand, it is preferably from 10 to 200, more preferably from 20 to 100, and still more preferably from 30 to 80.
於上述嵌段共聚物中,通式(III)所表示之結構單元之含有比例相對於上述嵌段共聚物之全部結構單元,較佳為30質量%以上95質量%以下,更佳為40質量%以上90質量%以下。In the above-mentioned block copolymer, the content ratio of the structural unit represented by the general formula (III) is preferably 30% by mass or more and 95% by mass or less, more preferably 40% by mass, relative to all the structural units of the above-mentioned block copolymer. % to 90% by mass.
包含通式(III)所表示之結構單元之嵌段部以作為溶劑親和性部位發揮功能之方式選擇即可,通式(III)所表示之結構單元可包含1種,亦可包含2種以上結構單元。於本發明之實施方式中,於通式(III)所表示之結構單元包含2種以上結構單元之情形時,於包含上述通式(III)所表示之結構單元之嵌段部內,2種以上結構單元可隨機排列。The block portion including the structural unit represented by the general formula (III) may be selected so as to function as a solvent-affinity site, and the structural unit represented by the general formula (III) may contain one type, or may contain two or more types Structural units. In an embodiment of the present invention, when the structural unit represented by the general formula (III) contains two or more structural units, in the block portion containing the structural unit represented by the above general formula (III), two or more Structural units can be randomly arranged.
於作為分散劑所使用之嵌段共聚物中,作為包含通式(I)所表示之結構單元之嵌段部的結構單元之單元數m與包含通式(III)所表示之結構單元之嵌段部的結構單元之單元數n之比率m/n,較佳為0.01以上1以下之範圍內,就色材之分散性、分散穩定性之方面而言,更佳為0.1以上0.7以下之範圍內。In the block copolymer used as a dispersant, the number of units m of the structural unit of the block portion comprising the structural unit represented by the general formula (I) and the number of blocks comprising the structural unit represented by the general formula (III) The ratio m/n of the unit number n of the structural unit of the segment is preferably in the range of 0.01 to 1, and in terms of the dispersibility and dispersion stability of the color material, it is more preferably in the range of 0.1 to 0.7 Inside.
作為上述嵌段共聚物之鍵結順序,只要具有包含上述通式(I)所表示之結構單元之嵌段部及包含通式(III)所表示之結構單元之嵌段部,且能夠使色材穩定地分散即可,並無特別限定,就與色材之相互作用優異,能夠有效地抑制分散劑彼此之凝集之方面而言,較佳為包含上述通式(I)所表示之結構單元之嵌段部僅鍵結於上述嵌段共聚物之一端。As the bonding order of the above-mentioned block copolymer, as long as it has a block part containing a structural unit represented by the above general formula (I) and a block part containing a structural unit represented by the general formula (III), and can make the color As long as the material is stably dispersed, it is not particularly limited. In terms of excellent interaction with the color material and the ability to effectively inhibit the aggregation of the dispersants, it is preferable to include the structural unit represented by the above general formula (I) The block part is bonded only to one end of the above-mentioned block copolymer.
上述嵌段共聚物之重量平均分子量並無特別限定,就使分散性變得良好、耐熱性優異之方面而言,較佳為2500以上500000以下,更佳為3000以上400000以下,進而更佳為6000以上300000以下。The weight average molecular weight of the block copolymer is not particularly limited, but is preferably from 2,500 to 500,000, more preferably from 3,000 to 400,000, and still more preferably More than 6,000 and less than 300,000.
具有上述通式(I)所表示之結構單元之聚合物之酸值就上述色材之分散性及保存穩定性之方面而言,較佳為20 mgKOH/g以上,更佳為30 mgKOH/g以上,進而較佳為40 mgKOH/g以上。另一方面,就顯影性優異之方面而言,具有上述通式(I)所表示之結構單元之聚合物之酸值較佳為150 mgKOH/g以下,更佳為120 mgKOH/g以下,進而較佳為100 mgKOH/g以下。 再者,於本發明中,酸值係指用以中和試樣1 g中所含之酸成分所需之氫氧化鉀之mg數,可依據JIS K 0070:1992進行測定。 The acid value of the polymer having the structural unit represented by the above-mentioned general formula (I) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g in terms of the dispersibility and storage stability of the above-mentioned color material Above, more preferably above 40 mgKOH/g. On the other hand, in terms of excellent developability, the acid value of the polymer having the structural unit represented by the above general formula (I) is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and further Preferably it is 100 mgKOH/g or less. In addition, in the present invention, the acid value refers to the number of mg of potassium hydroxide required to neutralize the acid component contained in 1 g of the sample, and can be measured in accordance with JIS K 0070:1992.
另一方面,作為上述含有羧基之嵌段共聚物,可包含如下嵌段共聚物,該嵌段共聚物含有包含源自(甲基)丙烯酸等含有羧基之乙烯性不飽和單體之結構單元之A嵌段與包含源自(甲基)丙烯酸烷基酯之結構單元之B嵌段。於含有羧基之嵌段共聚物中,包含源自(甲基)丙烯酸烷基酯之結構單元之B嵌段可與具有上述通式(I)所表示之結構單元之嵌段共聚物的包含上述通式(III)所表示之結構單元之嵌段部相同。On the other hand, as the above-mentioned carboxyl group-containing block copolymer, a block copolymer containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid can be included. An A block and a B block comprising structural units derived from alkyl (meth)acrylates. In the block copolymer containing a carboxyl group, the B block comprising a structural unit derived from an alkyl (meth)acrylate can be combined with the block copolymer comprising a structural unit represented by the above-mentioned general formula (I) The block portion of the structural unit represented by the general formula (III) is the same.
分散劑中之共聚物中之各結構單元之含有比例(莫耳%)可根據製造時原料之添加量來求出,又,可使用NMR等分析裝置進行測定。又,分散劑之結構可使用NMR、各種質量分析等進行測定。又,可視需要藉由熱分解等將分散劑分解,對於所獲得之分解物,使用高效液相層析法、氣相層析質譜儀、NMR、元素分析、XPS/ESCA(X-ray photoelectron spectroscopy/Electron Spectroscopy for Chemical Analysis,X射線光電子光譜/化學分析電子光譜)及TOF-SIMS(time of flight secondary ion mass spectrometry,飛行時間二次離子質譜儀)等而求出。The content ratio (mole %) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials added at the time of production, and can be measured using an analysis device such as NMR. Moreover, the structure of a dispersing agent can be measured using NMR, various mass spectrometry, etc. In addition, the dispersant may be decomposed by thermal decomposition or the like if necessary, and the obtained decomposed products are subjected to high performance liquid chromatography, gas chromatography mass spectrometry, NMR, elemental analysis, XPS/ESCA (X-ray photoelectron spectroscopy) /Electron Spectroscopy for Chemical Analysis, X-ray photoelectron spectroscopy/chemical analysis electron spectroscopy) and TOF-SIMS (time of flight secondary ion mass spectrometry, time of flight secondary ion mass spectrometry) and so on.
於本發明中,分散劑之含量根據所使用之色材之種類、進而下文所述之感光性著色樹脂組合物中之固形物成分濃度等適當選定即可。 分散劑之含量相對於感光性著色樹脂組合物之固形物成分總量,較佳為2質量%~30質量%之範圍內,更佳為3質量%~25質量%之範圍內。若為上述下限值以上,則色材之分散性及分散穩定性優異,感光性著色樹脂組合物之保存穩定性更優異。又,若為上述上限值以下,則顯影性變得良好。 In the present invention, the content of the dispersant may be appropriately selected according to the type of color material used, and furthermore, the solid content concentration in the photosensitive colored resin composition described below. The content of the dispersant is preferably within the range of 2% by mass to 30% by mass, more preferably within the range of 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. If it is more than the said lower limit, it will be excellent in the dispersibility and dispersion stability of a color material, and the storage stability of a photosensitive colored resin composition will be more excellent. Moreover, developability will become favorable as it is below the said upper limit.
[抗氧化劑] 本發明之感光性著色樹脂組合物就提高耐熱性、提高亮度之方面而言,較佳為進而含有抗氧化劑、及潛在性抗氧化劑之至少1種。 作為本發明所使用之抗氧化劑,並無特別限定,自先前公知者中適當選擇即可。作為抗氧化劑之具體例,例如可例舉:受阻酚系抗氧化劑、胺系抗氧化劑、磷系抗氧化劑、硫系抗氧化劑、肼系抗氧化劑等,就提高如線寬遮罩線寬之設計般形成細線圖案之能力之方面、及耐熱性之方面而言,較佳為使用受阻酚系抗氧化劑。 本發明所使用之潛在性抗氧化劑係具有能夠藉由加熱而脫離之保護基之化合物,該化合物藉由該保護基脫離而表現出抗氧化功能。其中,較佳為藉由在150℃以上進行加熱而保護基容易脫離者。作為本發明所使用之潛在性抗氧化劑,例如可例舉如國際公開第2014/021023號、國際公開第2017/170263號所記載之潛在性抗氧化劑。其中,可例舉受阻系酚系抗氧化劑之酚系羥基被保護基保護之潛在性抗氧化劑作為適宜者,更具體而言,可例舉藉由如第三丁氧基羰基之胺基甲酸酯系保護基取代受阻系酚系抗氧化劑之酚系羥基之氫而成之結構作為適宜者。 [Antioxidants] It is preferable that the photosensitive colored resin composition of this invention further contains at least 1 sort(s) of antioxidant and latent antioxidant from the point which improves heat resistance and brightness|luminance. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from previously known ones. Specific examples of antioxidants include, for example, hindered phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and hydrazine antioxidants. Generally, it is preferable to use a hindered phenolic antioxidant in terms of the ability to form a thin line pattern and in terms of heat resistance. The latent antioxidant used in the present invention is a compound having a protecting group that can be detached by heating, and the compound exhibits an antioxidant function through the detachment of the protecting group. Among them, preferred are those from which the protecting group can be easily detached by heating at 150° C. or higher. As the latent antioxidant used in the present invention, for example, those described in International Publication No. 2014/021023 and International Publication No. 2017/170263 may be mentioned. Among them, a latent antioxidant in which the phenolic hydroxyl group of the hindered phenolic antioxidant is protected by a protecting group is suitable, and more specifically, a carbamic acid such as a tertiary butoxycarbonyl group can be exemplified. The structure in which the hydrogen of the phenolic hydroxyl group of the hindered phenolic antioxidant is substituted with an ester-based protecting group is suitable.
作為受阻酚系抗氧化劑,例如可例舉:季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX1010,BASF公司製造)、異氰尿酸1,3,5-三(3,5-二第三丁基-4-羥基苄基)酯(商品名:Irganox 3114,BASF製造)、2,4,6-三(4-羥基-3,5-二第三丁基苄基)均三甲苯(商品名:Irganox 1330,BASF製造)、2,2'-亞甲基雙(6-第三丁基-4-甲基苯酚)(商品名:Sumilizer MDP-S,住友化學製造)、6,6'-硫代雙(2-第三丁基-4-甲基苯酚)(商品名:Irganox 1081,BASF製造)、3,5-二第三丁基-4-羥基苄基膦酸二乙酯(商品名:Irgamod 195,BASF製造)等。其中,就耐熱性及耐光性之方面而言,較佳為季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX1010,BASF公司製造)。As hindered phenolic antioxidants, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation),
抗氧化劑之含量相對於感光性著色樹脂組合物之固形物成分總量,較佳為0.1質量%~10.0質量%之範圍內,更佳為0.5質量%~5.0質量%之範圍內。若為上述下限值以上,則提高耐熱性、提高亮度之方面優異。另一方面,若為上述上限值以下,則能夠將本發明之著色樹脂組合物製成高感度之感光性樹脂組合物。The content of the antioxidant is preferably within a range of 0.1% by mass to 10.0% by mass, more preferably within a range of 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. When it is more than the said lower limit, it is excellent in the point which improves heat resistance and improves brightness. On the other hand, the colored resin composition of this invention can be made into the highly sensitive photosensitive resin composition as it is below the said upper limit.
[硫醇化合物] 本發明之感光性著色樹脂組合物就藉由較細之線寬提高顯影前後之膜厚變化之抑制效果之方面而言,較佳為進而含有硫醇化合物。 硫醇化合物由於烯硫醇反應不會受到氧引起之聚合抑制,故而表面硬化性優異,提高顯影殘膜率。硫醇化合物同時亦具有使線寬變粗之效果,但藉由組合使用紫外線吸收劑,而具有兼顧較細之線寬與提高顯影殘膜之協同效應。 作為硫醇化合物,可例舉硫醇基為1個之單官能硫醇化合物、硫醇基為2個以上之多官能硫醇基。就藉由較細之線寬提高顯影前後之膜厚變化之抑制效果之方面而言,更佳為使用多官能硫醇。 作為單官能硫醇化合物,例如可例舉:2-巰基苯并噻唑、2-巰基苯并㗁唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑、3-巰基丙酸、3-巰基丙酸甲酯、3-巰基丙酸乙酯、3-巰基丙酸辛酯等。 作為多官能硫醇化合物,例如可例舉:1,4-雙(3-巰基丁醯氧基)丁烷、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三𠯤-2,4,6(1H,3H,5H)-三酮、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、季戊四醇四(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、及四乙二醇雙(3-巰基丙酸酯)等。 作為硫醇化合物,可單獨使用或組合2種以上使用,其中,就藉由較細之線寬提高顯影前後之膜厚變化之抑制效果之方面而言,較佳為季戊四醇四(3-巰基丁酸酯)。 作為硫醇化合物之含量,相對於感光性著色樹脂組合物之固形物成分總量,通常為0.5質量%~10質量%,較佳為1質量%~5質量%之範圍內。若為上述下限值以上,則顯影前後之膜厚變化之抑制效果優異。另一方面,若為上述上限值以下,則容易將本發明之光硬化性紅色樹脂組合物製成顯影性良好且線寬偏移受到抑制者。 [thiol compound] It is preferable that the photosensitive colored resin composition of this invention further contains a thiol compound from the point which improves the suppression effect of the film thickness change before and after image development by a thinner line width. The thiol compound is not subject to polymerization inhibition by oxygen due to the enethiol reaction, so it has excellent surface hardening properties and increases the residual film rate of development. The thiol compound also has the effect of making the line width thicker, but by using the ultraviolet absorber in combination, it has a synergistic effect of taking into account the thinner line width and increasing the residual film after development. The thiol compound may, for example, be a monofunctional thiol compound having one thiol group or a polyfunctional thiol compound having two or more thiol groups. It is more preferable to use a multifunctional thiol from the point of view of enhancing the effect of suppressing the change in film thickness before and after development with a thinner line width. Examples of monofunctional thiol compounds include: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto -5-methoxybenzimidazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and the like. Examples of polyfunctional thiol compounds include: 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3 ,5-tris-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate), etc. As the thiol compound, it can be used alone or in combination of two or more. Among them, pentaerythritol tetrakis(3-mercaptobutyl) is preferred in terms of improving the effect of suppressing the change in film thickness before and after development due to the thinner line width. esters). As content of a thiol compound, it is 0.5 mass % - 10 mass % normally with respect to the solid content total amount of a photosensitive coloring resin composition, Preferably it exists in the range of 1 mass % - 5 mass %. When it is more than the said lower limit, the suppression effect of the film thickness change before and behind image development is excellent. On the other hand, it is easy to make the photocurable red resin composition of this invention favorable in developability as it is below the said upper limit, and line width shift is suppressed.
[其他成分] 本發明之感光性著色樹脂組合物可視需要含有各種添加劑。作為添加劑,例如可例舉:聚合終止劑、鏈轉移劑、調平劑、塑化劑、界面活性劑、消泡劑、矽烷偶合劑、密接促進劑等等。 作為界面活性劑及塑化劑之具體例,例如可例舉日本專利特開2013-029832號公報所記載者。 [other ingredients] The photosensitive colored resin composition of this invention may contain various additives as needed. As an additive, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an adhesion promoter, etc. are mentioned, for example. As a specific example of a surfactant and a plasticizer, what was described in Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.
<感光性著色樹脂組合物之製造方法> 本發明之感光性著色樹脂組合物之製造方法可藉由使用公知之混合方法將色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、溶劑、及根據所需所使用之分散劑等或各種添加成分加以混合而製備。 作為該樹脂組合物之製備方法,例如可例舉:(1)首先於溶劑中添加色材、及分散劑而製備色材分散液,並於該分散液中混合鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及根據所需所使用之各種添加成分之方法;(2)於溶劑中同時投入色材、鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及根據所需所使用之各種添加成分並加以混合之方法;(3)於溶劑中添加鹼可溶性樹脂、光聚合性化合物、光起始劑、紫外線吸收劑、及根據所需所使用之分散劑等或各種添加成分並加以混合後,添加色材使其分散之方法;(4)於溶劑中添加色材、分散劑、及鹼可溶性樹脂而製備色材分散液,並於該分散液中進一步添加鹼可溶性樹脂、溶劑、光聚合性化合物、光起始劑、紫外線吸收劑、及根據所需所使用之各種添加成分並加以混合之方法;等。 該等方法中,就可有效地防止色材之凝集而使其均勻地分散之方面而言,較佳為上述(1)及(4)之方法。 <Manufacturing method of photosensitive colored resin composition> The production method of the photosensitive colored resin composition of the present invention can be by using a known mixing method to mix a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, a solvent, and as required It is prepared by mixing the dispersant, etc. or various additives. As the preparation method of the resin composition, for example: (1) First, add a color material and a dispersant to a solvent to prepare a color material dispersion, and mix an alkali-soluble resin and a photopolymerizable compound in the dispersion , photoinitiator, ultraviolet absorber, and the method of adding various ingredients according to the needs; (3) Add alkali-soluble resin, photopolymerizable compound, photoinitiator, ultraviolet absorber, and A method of adding a color material to disperse after mixing the dispersant or various additional components; (4) adding a color material, a dispersant, and an alkali-soluble resin to a solvent to prepare a color material dispersion, and adding the color material to the dispersion liquid A method of further adding an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and various additional components used as required and mixing them; etc. Among these methods, the above-mentioned methods (1) and (4) are preferable in terms of effectively preventing aggregation of coloring materials and uniformly dispersing them.
製備色材分散液之方法可自先前公知之分散方法中適當選擇使用。 作為用以進行分散處理之分散機,可例舉:雙輥研磨機、三輥研磨機等輥磨機;球磨機、振動球磨機等球磨機;塗料調節器、連續盤型珠磨機、連續環形珠磨機等珠磨機。作為珠磨機之較佳之分散條件,所使用之珠徑較佳為0.03 mm~2.00 mm,更佳為0.10 mm~1.0 mm。 The method for preparing the color material dispersion can be appropriately selected from previously known dispersion methods. Examples of dispersing machines for dispersing treatment include roller mills such as two-roll mills and three-roll mills; ball mills such as ball mills and vibrating ball mills; paint conditioners, continuous disc bead mills, and continuous ring bead mills. machine and other bead mills. As a preferred dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
[用途] 本發明之感光性著色樹脂組合物係含有三芳基甲烷系染料之色澱色材且能夠形成提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層,因此能夠適宜地用於彩色濾光片用途。 [use] The photosensitive colored resin composition of the present invention is a lake color material containing a triarylmethane dye and can form a colored layer that improves brightness and suppresses changes in film thickness before and after development with a thinner line width, so it can be suitably used For color filter applications.
[感光性著色樹脂組合物之硬化物] 本發明之硬化物為上述本發明之感光性著色樹脂組合物之硬化物。 本發明之硬化物可藉由形成上述本發明之感光性著色樹脂組合物之塗膜,使該塗膜乾燥後進行曝光、及顯影而獲得。作為塗膜之形成、曝光、及顯影之方法,例如可設為與下文所述之本發明之彩色濾光片所具備之著色層之形成中所使用之方法同樣之方法。 又,本發明之硬化物係含有三芳基甲烷系染料之色澱色材且提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層,可適宜地用作彩色濾光片之著色層。 [Cured product of photosensitive colored resin composition] The cured product of the present invention is a cured product of the above-mentioned photosensitive colored resin composition of the present invention. The cured product of the present invention can be obtained by forming a coating film of the above-mentioned photosensitive colored resin composition of the present invention, drying the coating film, and performing exposure and development. As the method of forming, exposing, and developing the coating film, for example, the same method as the method used for forming the colored layer included in the color filter of the present invention described below can be used. In addition, the hardened product of the present invention is a coloring layer containing a triarylmethane-based dye lake material that increases brightness and suppresses changes in film thickness before and after development with a thinner line width, and can be suitably used as a color filter The coloring layer.
III.彩色濾光片 本發明之彩色濾光片係至少具備基板、及設置於該基板上之著色層之彩色濾光片,該著色層之至少一者為上述本發明之感光性著色樹脂組合物之硬化物。 III. Color filter The color filter of the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, at least one of which is a cured product of the photosensitive colored resin composition of the present invention.
參照圖對此種本發明之彩色濾光片進行說明。圖1係表示本發明之彩色濾光片之一例之概略截面圖。根據圖1,本發明之彩色濾光片10具有基板1、遮光部2、及著色層3。Such a color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1 , a
[著色層] 本發明之彩色濾光片所使用之著色層係至少一者為上述本發明之感光性著色樹脂組合物之硬化物之著色層。 著色層通常形成於下文所述之基板上之遮光部之開口部,通常包含3色以上之著色圖案。 又,作為該著色層之排列,並無特別限定,例如可設為條紋型、馬賽克型、三角型、4像素配置型等通常之排列。又,著色層之寬度、面積等可任意設定。 該著色層之厚度可藉由調整塗佈方法、感光性著色樹脂組合物之固形物成分濃度或黏度等來適當控制,通常較佳為1~5 μm之範圍。 [coloring layer] At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the substrate described below, and usually includes colored patterns of three or more colors. In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a 4-pixel arrangement type can be used. In addition, the width, area, etc. of the colored layer can be set arbitrarily. The thickness of the colored layer can be properly controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition, etc., and is usually preferably in the range of 1-5 μm.
該著色層例如可藉由下述方法形成。 首先,使用噴塗法、浸漬塗佈法、棒式塗佈法、輥式塗佈法、旋轉塗佈法、模嘴塗佈法等塗佈方法將上文所述之本發明之感光性著色樹脂組合物塗佈於下文所述之基板上,形成濕式塗膜。其中,可適當地使用旋轉塗佈法、模嘴塗佈法。 其次,使用加熱板或烘箱等將該濕式塗膜乾燥後,介隔規定圖案之遮罩對其進行曝光,使鹼可溶性樹脂及多官能單體等進行光聚合反應而製成硬化塗膜。作為曝光所使用之光源,例如可例舉:低壓水銀燈、高壓水銀燈、金屬鹵化物燈等紫外線、電子束等。曝光量可根據所使用之光源或塗膜之厚度等適當調整。 又,於曝光後,為了促進聚合反應,亦可進行加熱處理。加熱條件可根據所使用之感光性著色樹脂組合物中之各成分之調配比例或塗膜之厚度等適當選擇。 This colored layer can be formed by the following method, for example. First, the above-mentioned photosensitive colored resin of the present invention is coated by spray coating, dip coating, rod coating, roll coating, spin coating, die coating and other coating methods. The compositions were coated on the substrates described below to form wet coating films. Among them, a spin coating method and a die coating method can be suitably used. Next, after drying the wet coating film using a hot plate or an oven, etc., it is exposed through a mask with a predetermined pattern, and the alkali-soluble resin and multifunctional monomer are photopolymerized to form a cured coating film. As a light source used for exposure, ultraviolet rays, such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, electron beam, etc. are mentioned, for example. The exposure amount can be adjusted appropriately according to the light source used or the thickness of the coating film. Moreover, after exposure, you may heat-process in order to accelerate a polymerization reaction. Heating conditions can be appropriately selected according to the compounding ratio of each component in the photosensitive colored resin composition used, the thickness of a coating film, etc.
繼而,使用顯影液進行顯影處理,將未曝光部分溶解、去除,藉此以所需之圖案形成塗膜。作為顯影液,通常使用將鹼溶解於水或水溶性溶劑中而成之溶液。亦可於該鹼溶液中適量添加界面活性劑等。又,顯影方法可採用通常之方法。 顯影處理後通常進行顯影液之洗淨、感光性著色樹脂組合物之硬化塗膜之乾燥,而形成著色層。再者,於顯影處理後,為了使塗膜充分硬化,亦可進行加熱處理。作為加熱條件,並無特別限定,可根據塗膜之用途適當選擇。 Next, a developing treatment is performed using a developing solution to dissolve and remove unexposed parts, thereby forming a coating film in a desired pattern. As a developing solution, a solution obtained by dissolving an alkali in water or a water-soluble solvent is generally used. A suitable amount of surfactant or the like may also be added to the alkaline solution. In addition, as a developing method, a usual method can be used. After the development treatment, washing of the developing solution and drying of the cured coating film of the photosensitive colored resin composition are usually carried out to form a colored layer. In addition, heat processing may be performed in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited, and may be appropriately selected according to the application of the coating film.
[遮光部] 本發明之彩色濾光片中之遮光部係於下文所述之基板上以圖案狀形成者,可設為與通常之彩色濾光片中作為遮光部所使用者相同。 作為該遮光部之圖案形狀,並無特別限定,例如可例舉:條紋狀、矩陣狀等形狀。遮光部可為藉由濺鍍法、真空蒸鍍法等獲得之鉻等之金屬薄膜。或者遮光部可為於樹脂黏合劑中含有碳微粒子、金屬氧化物、無機顏料、有機顏料等遮光性粒子之樹脂層。於含有遮光性粒子之樹脂層之情形時,有使用感光性抗蝕劑藉由顯影進行圖案化之方法、使用含有遮光性粒子之噴墨油墨進行圖案化之方法、將感光性抗蝕劑熱轉印之方法等。 [shading department] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate described below, and can be set to be the same as that used as the light-shielding portion in a normal color filter. It does not specifically limit as a pattern shape of this light shielding part, For example, shapes, such as a stripe shape and a matrix shape, are mentioned. The light-shielding portion may be a metal thin film of chromium or the like obtained by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon microparticles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and heating a photosensitive resist. Method of transfer, etc.
作為遮光部之膜厚,於金屬薄膜之情形時,設定為0.2~0.4 μm左右,於為使黑色顏料分散或溶解於黏合劑樹脂中而成者之情形時,設定為0.5~2 μm左右。The film thickness of the light-shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and set to about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin.
[基板] 作為基板,可使用下文所述之透明基板、矽基板、及於透明基板或矽基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。可於該等基板上形成其他彩色濾光片層、樹脂層、TFT(thin-film transistor,薄膜電晶體)等電晶體、電路等。 作為本發明之彩色濾光片中之透明基板,只要為對可見光而言透明之基材即可,並無特別限定,可使用通常之彩色濾光片所使用之透明基板。具體而言,可例舉:石英玻璃、無鹼玻璃、合成石英板等無可撓性之透明之剛性材或透明樹脂膜、光學用樹脂板、軟性玻璃等具有可撓性之透明之軟性材。 該透明基板之厚度並無特別限定,可根據本發明之彩色濾光片之用途,而使用例如100 μm~1 mm左右者。 再者,本發明之彩色濾光片除了上述基板、遮光部及著色層以外,亦可為例如外覆層或透明電極層、進而形成有配向膜或柱狀間隔件等者。 [substrate] As the substrate, a transparent substrate described below, a silicon substrate, and a thin film of aluminum, silver, silver/copper/palladium alloy, etc. formed on a transparent substrate or a silicon substrate can be used. Other color filter layers, resin layers, TFT (thin-film transistor, thin-film transistor) and other transistors, circuits, etc. can be formed on these substrates. The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in ordinary color filters can be used. Specifically, examples include non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent resin films, optical resin plates, and flexible transparent soft materials such as flexible glass. . The thickness of the transparent substrate is not particularly limited, and depending on the use of the color filter of the present invention, for example, a thickness of about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may be, for example, an overcoat layer or a transparent electrode layer, and further formed with an alignment film or a columnar spacer, in addition to the above-mentioned substrate, light-shielding portion, and colored layer.
IV.顯示裝置 本發明之顯示裝置之特徵在於具有上述本發明之彩色濾光片。於本發明中,顯示裝置之構成並無特別限定,可自先前公知之顯示裝置中適當選擇,例如可例舉液晶顯示裝置、或有機發光顯示裝置等。 IV. Display device A display device of the present invention is characterized by comprising the above-mentioned color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from previously known display devices, for example, a liquid crystal display device or an organic light-emitting display device.
[液晶顯示裝置]
作為本發明之液晶顯示裝置,例如可例舉具有上文所述之本發明之彩色濾光片、對向基板、及形成於上述彩色濾光片與上述對向基板之間之液晶層之液晶顯示裝置。
參照圖對此種本發明之液晶顯示裝置進行說明。圖2係表示本發明之液晶顯示裝置之一例的概略圖。如圖2所例示,本發明之液晶顯示裝置40具有彩色濾光片10、包含TFT陣列基板等之對向基板20、及形成於上述彩色濾光片10與上述對向基板20之間之液晶層30。
再者,本發明之液晶顯示裝置並不限定於該圖2所示之構成,可設為通常作為使用彩色濾光片之液晶顯示裝置所公知之構成。
[Liquid crystal display device]
As the liquid crystal display device of the present invention, for example, a liquid crystal having the above-mentioned color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate can be exemplified. display device.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As shown in FIG. 2, the liquid
作為本發明之液晶顯示裝置之驅動方式,並無特別限定,可採用通常用於液晶顯示裝置之驅動方式。作為此種驅動方式,例如可例舉:TN(Twisted Nematic,扭轉向列)方式、IPS(In-Plane Switching,橫向電場效應)方式、OCB(optically compensated bend,光學補償彎曲)方式、及MVA(Multi-Domain Vertical Alignment,多域垂直配向)方式等。於本發明中,可適宜地使用該等之任一方式。 又,作為對向基板,可根據本發明之液晶顯示裝置之驅動方式等適當選擇而使用。 進而,作為構成液晶層之液晶,可根據本發明之液晶顯示裝置之驅動方式等,使用介電各向異性不同之各種液晶、及該等之混合物。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be employed. As such a driving method, for example, a TN (Twisted Nematic) method, an IPS (In-Plane Switching, transverse electric field effect) method, an OCB (optically compensated bend) method, and an MVA ( Multi-Domain Vertical Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these modes can be suitably used. In addition, as a counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention, and the like. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention and the like.
作為液晶層之形成方法,可使用通常作為液晶單元之製作方法所使用之方法,例如可例舉真空注入方式或液晶滴加方式等。於藉由上述方法形成液晶層後,將液晶單元緩冷至常溫,藉此可使所封入之液晶配向。As a method for forming a liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, for example, a vacuum injection method or a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal unit is slowly cooled to room temperature, thereby aligning the sealed liquid crystal.
[有機發光顯示裝置]
作為本發明之有機發光顯示裝置,例如可例舉具有上文所述之本發明之彩色濾光片、及有機發光體之有機發光顯示裝置。
參照圖對此種本發明之有機發光顯示裝置進行說明。圖3係表示本發明之有機發光顯示裝置之一例的概略圖。如圖3所例示,本發明之有機發光顯示裝置100具有彩色濾光片10、及有機發光體80。可於彩色濾光片10與有機發光體80之間具有有機保護層50或無機氧化膜60。
[Organic Light Emitting Display Device]
As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter of the present invention and an organic light-emitting body can be exemplified.
The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. As shown in FIG. 3 , the organic light emitting
作為有機發光體80之積層方法,例如可例舉:於彩色濾光片上表面依次形成透明陽極71、電洞注入層72、電洞傳輸層73、發光層74、電子注入層75、及陰極76之方法;或將於其他基板上形成之有機發光體80貼合於無機氧化膜60上之方法等。有機發光體80中之透明陽極71、電洞注入層72、電洞傳輸層73、發光層74、電子注入層75、及陰極76、其他構成可適當使用公知者。以上述方式所製作之有機發光顯示裝置100例如可應用於被動驅動方式之有機EL顯示器,亦可應用於主動驅動方式之有機EL顯示器。
再者,本發明之有機發光顯示裝置並不限定於該圖3所示之構成,可設為通常作為使用彩色濾光片之有機發光顯示裝置所公知之構成。
實施例
As a lamination method of the organic
以下,示出實施例對本發明進行具體說明。該等記載並不對本發明進行限制。 鹽形成前之共聚物之質量平均分子量(Mw)可依據上文所述之本發明之說明書所記載之測定方法,藉由GPC(凝膠滲透層析法)以標準聚苯乙烯換算值之形式求出。 Hereinafter, an Example is shown and this invention is demonstrated concretely. These descriptions do not limit the present invention. The mass-average molecular weight (Mw) of the copolymer before salt formation can be expressed as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention described above. Find out.
[紫外線吸收劑於PGMEA中之溶解性試驗] 紫外線吸收劑於PGMEA中之溶解性試驗係於25℃量取各紫外線吸收劑0.5 g,添加至PGMEA 9.5 g中,利用攪拌器攪拌1小時後,藉由目視進行評價。 〇:無溶解殘留 ×:有溶解殘留 [Solubility test of UV absorber in PGMEA] The solubility test of ultraviolet absorbers in PGMEA measured 0.5 g of each ultraviolet absorber at 25° C., added to 9.5 g of PGMEA, stirred with a stirrer for 1 hour, and evaluated visually. 〇: No dissolved residue ×: Dissolution remains
[紫外線吸收劑之波長365 nm下之透過率之測定] 紫外線吸收劑之波長365 nm下之透過率係製備各紫外線吸收劑之0.002質量%丙二醇單甲醚乙酸酯溶液,使用紫外可見近紅外分光光度計(例如日本分光股份有限公司之V-7100)測定該0.002質量%丙二醇單甲醚乙酸酯溶液。 將紫外線吸收劑之波長365 nm下之透過率之測定結果示於表1。 [Measurement of the transmittance of ultraviolet absorbers at a wavelength of 365 nm] The transmittance of the ultraviolet absorber at a wavelength of 365 nm is prepared by preparing 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber, using a UV-visible-near-infrared spectrophotometer (such as V-7100 of JASCO Co., Ltd.) This 0.002 mass % propylene glycol monomethyl ether acetate solution was measured. Table 1 shows the measurement results of the transmittance of the ultraviolet absorber at a wavelength of 365 nm.
[表1]
(合成例1:色澱色材1之合成)
(1)中間物1之合成
參照日本專利特開2018-3013號所記載之中間物A-2、中間物B-1、及化合物1-3之製造方法,獲得下述化學式(a)所表示之中間物1(產率87%)。
根據下述分析結果,確認到所獲得之化合物為目標化合物。
・MS(ESI) (m/z):677(+)、二價
・元素分析值:CHN(Carbon-Hydrogen-Nitrogen,碳氫氮)實測值 (81.81%、7.31%、5.85%);理論值(81.77%、7.36%、5.90%)
(Synthesis Example 1: Synthesis of Lake Color Material 1)
(1) Synthesis of
[化13] [chemical 13]
(2)色澱色材1之合成
將關東化學製造之12鎢磷酸-n水合物2.59 g(0.76 mmol)加熱溶解於甲醇40 mL、水40 mL之混合液中,添加1.6 g(1.19 mmol)之上述中間物1,並攪拌1小時。濾取沈澱物,以水將其洗淨。將所獲得之沈澱物於減壓下加以乾燥,而獲得下述化學式(b)所表示之色澱色材1(產率95%)。
根據下述分析結果,確認到所獲得之化合物為目標化合物。
・31P NMR(d-dmso、ppm)δ-15.15
・MS(MALDI) (m/z):1355(M
+)、2879(MH
2 -)
・元素分析值:CHN實測值 (35.55%、3.24%、2.61%);理論值(35.61%、3.20%、2.57%)
・螢光X射線分析:MoW實測比(0%、100%);理論值(0%、100%)
(2) Synthesis of
[化14] [chemical 14]
(合成例2:色澱色材2之合成) (1)K
6(P
2MoW
17O
62)之製備
將NaWO
4・2H
2O(和光純藥工業製造)44.0 g、Na
2MoO
4・2H
2O(關東化學製造)1.90 g溶解於純化水230 g中。使用滴加漏斗一面攪拌一面於該溶液中添加85%磷酸64.9 g。將所獲得之溶液加熱回流8小時。將反應液冷卻為室溫,添加1滴溴水,一面攪拌一面添加氯化鉀45 g。進而攪拌1小時後,將沈澱物過濾分離。於90℃將所獲得之固體加以乾燥,藉此獲得29.4 g之K
6(P
2MoW
17O
62)。
(2)色澱色材2之合成
將C.I.鹼性藍7(BB7)(東京化成製造)5.30 g投入純化水350 ml中,於40℃加以攪拌進行溶解,而製備BB7溶液。另外地,將上述(1)中所製備之K
6(P
2MoW
17O
62)10.0 g溶解於純化水40 ml中。於BB7溶液中投入K
6(P
2MoW
17O
62)溶液,直接於40℃攪拌1小時。繼而,將內溫上升為80℃,進一步攪拌1小時而進行色澱化。冷卻後進行過濾,利用300 ml之純化水洗淨3次。將所獲得之固體於90℃加以乾燥,藉此以黑藍色固體之形式獲得10.4 g之平均一次粒徑為40 nm之作為三芳基甲烷系染料與多酸之色澱色材的色澱色材2。
(Synthesis Example 2: Synthesis of Lake Color Material 2) (1) Preparation of K 6 (P 2 MoW 17 O 62 ) NaWO 4 ·2H 2 O (manufactured by Wako Pure Chemical Industries) 44.0 g, Na 2 MoO 4 · 1.90 g of 2H 2 O (manufactured by Kanto Chemical Industry) was dissolved in 230 g of purified water. 64.9 g of 85% phosphoric acid was added to this solution, stirring using the dropping funnel. The resulting solution was heated to reflux for 8 hours. The reaction liquid was cooled to room temperature, 1 drop of bromine water was added, and 45 g of potassium chloride was added while stirring. After further stirring for 1 hour, the precipitate was separated by filtration. The obtained solid was dried at 90°C, whereby 29.4 g of K 6 (P 2 MoW 17 O 62 ) was obtained. (2) Synthesis of
(合成例3:酸性分散劑A1(具有選自上述通式(I)所表示之結構單元中之至少1種之聚合物)之合成) (1)巨單體MM-1之合成 於具備冷凝管、添加用漏斗、氮氣用入口、機械攪拌機、數位溫度計之反應器中加入丙二醇單甲醚乙酸酯(簡稱PGMEA)80.0質量份,於氮氣氣流下一面攪拌,一面將溫度加溫為90℃。歷經1.5小時滴加甲基丙烯酸甲酯50.0質量份、甲基丙烯酸正丁酯30.0質量份、甲基丙烯酸苄酯20.0質量份、2-巰基乙醇4.0質量份、PGMEA 30質量份、α,α'-偶氮二異丁腈(簡稱AIBN)1.0質量份之混合溶液,進一步反應3小時。繼而,停止氮氣氣流,將該反應溶液冷卻為80℃,添加Karenz MOI(昭和電工製造)8.74質量份、二月桂酸二丁基錫0.125質量份、對甲氧基苯酚0.125質量份、及PGMEA 10質量份,並攪拌3小時,藉此獲得巨單體MM-1之49.5質量%溶液。所獲得之巨單體MM-1進行GPC測定之結果為質量平均分子量(Mw)為4010,數量平均分子量(Mn)為1910,分子量分佈(Mw/Mn)為2.10。 (Synthesis Example 3: Synthesis of Acidic Dispersant A1 (a polymer having at least one structural unit selected from the above-mentioned general formula (I))) (1) Synthesis of macromonomer MM-1 Add 80.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA for short) to a reactor equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heat while stirring under a nitrogen stream. is 90°C. 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of 2-mercaptoethanol, 30 parts by mass of PGMEA, α,α' were added dropwise over 1.5 hours - A mixed solution of 1.0 parts by mass of azobisisobutyronitrile (abbreviated as AIBN), further reacted for 3 hours. Next, the flow of nitrogen gas was stopped, the reaction solution was cooled to 80° C., and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko), 0.125 parts by mass of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and 10 parts by mass of PGMEA were added. , and stirred for 3 hours, thereby obtaining a 49.5% by mass solution of the macromonomer MM-1. As a result of GPC measurement of the obtained macromonomer MM-1, the mass average molecular weight (Mw) was 4010, the number average molecular weight (Mn) was 1910, and the molecular weight distribution (Mw/Mn) was 2.10.
(2)接枝共聚物A1之合成 於具備冷凝管、添加用漏斗、氮氣用入口、機械攪拌機、數位溫度計之反應器中加入PGMEA 85.0質量份,於氮氣氣流下一面攪拌,一面將溫度加溫為90℃。歷經1.5小時滴加上述巨單體MM-1溶液67.34質量份(固形物成分33.33質量份)、甲基丙烯酸縮水甘油酯(簡稱GMA)16.67質量份、正十二烷基硫醇1.24質量份、PGMEA 25.0質量份、AIBN 0.5質量份之混合溶液,加熱攪拌3小時後,歷經10分鐘滴加AIBN 0.10質量份 、PGMEA 10.0質量份之混合液,進一步於相同溫度下熟化1小時,藉此獲得接枝共聚物A1之25.0質量%溶液。所獲得之接枝共聚物A1進行GPC測定之結果為質量平均分子量(Mw)為10570,數量平均分子量(Mn)為4370,分子量分佈(Mw/Mn)為2.42。 (2) Synthesis of graft copolymer A1 Add 85.0 parts by mass of PGMEA to a reactor equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and heat the temperature to 90°C while stirring under a nitrogen stream. After 1.5 hours, 67.34 parts by mass of the above-mentioned macromonomer MM-1 solution (33.33 parts by mass of solid content), 16.67 parts by mass of glycidyl methacrylate (abbreviated as GMA), 1.24 parts by mass of n-dodecyl mercaptan, A mixed solution of 25.0 parts by mass of PGMEA and 0.5 parts by mass of AIBN was heated and stirred for 3 hours, then a mixed solution of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was added dropwise over 10 minutes, and further aged at the same temperature for 1 hour, thereby obtaining 25.0 mass % solution of branch copolymer A1. As a result of GPC measurement of the obtained graft copolymer A1, the mass average molecular weight (Mw) was 10570, the number average molecular weight (Mn) was 4370, and the molecular weight distribution (Mw/Mn) was 2.42.
(3)具有選自上述通式(I)所表示之結構單元中之至少1種之聚合物(酸性分散劑A1)之製造 於具備冷凝管、添加用漏斗、氮氣用入口、機械攪拌機、數位溫度計之反應器中加入PGMEA 27.80質量份、苯基膦酸(製品名「PPA」,日產化學製造)9.27質量份,於氮氣氣流下一面攪拌,一面將溫度加溫為90℃。 歷經30分鐘滴加上述接枝共聚物A1之100.0質量份,加熱攪拌2小時,藉此獲得具有選自上述通式(I)所表示之結構單元中之至少1種之聚合物(酸性分散劑A1)溶液(固形物成分25.0質量%)。藉由酸值測定及 1H-NMR測定確認到所獲得之酸性分散劑A1之GMA與PPA之酯化反應之進行(確認到源自環氧基之峰消失)。所獲得之酸性分散劑A1之酸值為98 mgKOH/g。 (3) Manufacture of a polymer (acidic dispersant A1) having at least one structural unit selected from the above-mentioned general formula (I) on a device equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital 27.80 parts by mass of PGMEA and 9.27 parts by mass of phenylphosphonic acid (product name "PPA", manufactured by Nissan Chemical) were added to the reactor of the thermometer, and the temperature was heated to 90°C while stirring under a nitrogen stream. 100.0 parts by mass of the above-mentioned graft copolymer A1 was added dropwise over 30 minutes, heated and stirred for 2 hours, thereby obtaining a polymer (acidic dispersant A1) Solution (solid content: 25.0% by mass). The progress of the esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was confirmed by the acid value measurement and 1 H-NMR measurement (it confirmed that the peak originating in an epoxy group disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.
(合成例4::酸性分散劑A2(含有包含源自含有羧基之乙烯性不飽和單體之結構單元的A嵌段與包含源自(甲基)丙烯酸烷基酯之結構單元之B嵌段的嵌段共聚物)之合成)
參照國際公開第2016/132863號所記載之實施例1,合成具有甲基丙烯酸甲酯(MMA)20質量份、甲基丙烯酸正丁酯(BMA)40質量份之嵌段、甲基丙烯酸(MAA)20質量份、BMA 20質量份之嵌段、及MMA 20質量份、BMA 40質量份之嵌段的三嵌段共聚物。所獲得之嵌段共聚物之重量平均分子量(Mw)為11000,分子量分佈(Mw/Mn)為1.50,酸值為130 mgKOH/g。
(Synthesis example 4:: Acidic dispersant A2 (contains A block comprising a structural unit derived from a carboxyl-containing ethylenically unsaturated monomer and a B block comprising a structural unit derived from an alkyl (meth)acrylate Synthesis of block copolymers)
Referring to Example 1 described in International Publication No. 2016/132863, a block having 20 parts by mass of methyl methacrylate (MMA), 40 parts by mass of n-butyl methacrylate (BMA), and methacrylic acid (MAA) were synthesized. ) 20 mass parts,
(合成例5:潛在性抗氧化劑之合成) 將下述化學式(c)所表示之酚化合物0.01 mol、二碳酸二第三丁酯0.05 mol及吡啶30 g混合,於氮氣環境、室溫下添加4-二甲胺基吡啶0.025 mol,於60℃攪拌3小時。冷卻至室溫後,將反應液注入離子交換水150 g中,添加氯仿200 g進行油水分離。利用無水硫酸鈉將有機層乾燥後,將溶劑蒸餾去除,於殘渣中添加甲醇100 g進行晶析。於60℃將所獲得之白色粉狀結晶減壓乾燥3小時,獲得潛在性抗氧化劑(化合物A)。再者,所獲得之潛在性抗氧化劑之結構係藉由IR及NMR進行確認。 (Synthesis Example 5: Synthesis of Potential Antioxidants) Mix 0.01 mol of phenol compound represented by the following chemical formula (c), 0.05 mol of di-tert-butyl dicarbonate and 30 g of pyridine, add 0.025 mol of 4-dimethylaminopyridine under nitrogen atmosphere and room temperature, °C and stirred for 3 hours. After cooling to room temperature, the reaction solution was poured into 150 g of ion-exchanged water, and 200 g of chloroform was added for oil-water separation. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off, 100 g of methanol was added to the residue, and crystallization was performed. The obtained white powdery crystals were dried under reduced pressure at 60° C. for 3 hours to obtain a potential antioxidant (compound A). Furthermore, the structures of the obtained potential antioxidants were confirmed by IR and NMR.
[化15] [chemical 15]
(比較合成例1:三芳基甲烷系染料1之合成)
以與日本專利特開2011-133844號之實施例1所記載之染料A同樣之方式,合成三芳基甲烷系染料1。
首先,如日本專利特開2011-133844號之實施例1所記載般,合成(甲苯磺醯基)三氟甲磺醯亞胺酸三乙胺鹽。
繼而,將C.I.鹼性藍7(N-[4-[[4-(二乙胺基)苯基][4-(乙基胺基)-1-萘基]亞甲基]-2,5-環己二烯-1-亞基]-N-乙基乙烷銨-氯化物)(東京化成製造)5 g溶解於甲醇30 mL中,一面攪拌一面添加(甲苯磺醯基)三氟甲磺醯亞胺酸三乙胺鹽3.93 g,進而於室溫下攪拌1小時。利用蒸發器將溶液中之甲醇濃縮,添加水100 mL,濾取沈澱物,以水將其洗淨。將該濾餅進行減壓乾燥,而獲得三芳基甲烷系染料1。
(Comparative Synthesis Example 1: Synthesis of Triarylmethane Dye 1)
Triarylmethane-based
(製備例1:鹼可溶性樹脂P1之製備)
於聚合槽中加入300質量份之PGMEA,於氮氣環境下升溫為100℃後,歷經1.5小時連續滴加甲基丙烯酸苄酯(BzMA)67.6質量份、MMA 67.6質量份、甲基丙烯酸(MAA)36.4質量份及PERBUTYL O(日油製造)3質量份、鏈轉移劑(正十二烷基硫醇)9質量份。其後,保持100℃繼續反應,於上述主鏈形成用混合物之滴加結束起2小時後添加作為聚合抑制劑之對甲氧基苯酚0.1質量份而使聚合停止。
繼而,一面吹入空氣,一面添加作為含有環氧基之化合物之甲基丙烯酸縮水甘油酯(GMA)28.4質量份,升溫為110℃後,添加三乙胺0.8質量份,於110℃加成反應15小時,而獲得鹼可溶性樹脂P1溶液(重量平均分子量(Mw)9000,酸值75 mgKOH/g,固形物成分40質量%)。
再者,上述重量平均分子量之測定方法係以聚苯乙烯作為標準物質,以THF(tetrahydrofuran,四氫呋喃)作為溶離液,藉由ShodexGPC系統-21H(Shodex GPC System-21H)測定重量平均分子量。又,酸值之測定方法係基於JIS K 0070進行測定。
(Preparation Example 1: Preparation of Alkali-soluble Resin P1)
Add 300 parts by mass of PGMEA to the polymerization tank, and after raising the temperature to 100°C under a nitrogen atmosphere, continuously drop 67.6 parts by mass of benzyl methacrylate (BzMA), 67.6 parts by mass of MMA, and methacrylic acid (MAA) dropwise over 1.5 hours 36.4 parts by mass, 3 parts by mass of PERBUTYL O (manufactured by NOF), and 9 parts by mass of a chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued while maintaining 100° C., and 0.1 parts by mass of p-methoxyphenol was added as a
(實施例1:感光性著色樹脂組合物1之製造)
(1)色材分散液1之製備
於225 mL蛋黃醬瓶中裝入PGMEA 61質量份、製備例1之鹼可溶性樹脂P1溶液(固形物成分40質量%)5質量份、合成例3之酸性分散劑A1溶液(固形物成分25.0質量%)24質量份並加以攪拌。
向其中裝入10質量份之合成例1之三芳基甲烷系色澱色材1、100質量份之粒徑2.0 mm之氧化鋯珠,利用塗料振盪機(淺田鐵工公司製造)振盪1小時作為預碎解,繼而變更為粒徑0.1 mm之氧化鋯珠200份,利用塗料振盪機進行4小時分散作為正式碎解,而獲得色材分散液1。
(Example 1: Manufacture of Photosensitive Colored Resin Composition 1)
(1) Preparation of
(2)感光性黏合劑成分B1之製備
添加製備例1中所獲得之鹼可溶性樹脂P1溶液(固形物成分40質量%)26.5質量份、光聚合性化合物(商品名ARONIX M-403,二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯,東亞合成製造)17.7質量份、光聚合性化合物(商品名ARONIX M-305,季戊四醇三丙烯酸酯及季戊四醇四丙烯酸酯,東亞合成製造)7.06質量份、作為光起始劑之光起始劑1(I1):Irgacure 907(BASF製造,α-胺基苯乙酮系光起始劑)1.96質量份及光起始劑2(I2):OXE-02(BASF製造,具有咔唑骨架之肟酯系光起始劑)1.96質量份、紫外線吸收劑(紫外線吸收劑1(U1):Kemisorb71,Chemipro Kasei製造)0.392質量份、作為抗氧化劑之IRGANOX1010(BASF製造)0.392質量份、PGMEA 44.1質量份,而獲得感光性黏合劑成分B1。
(3)感光性著色樹脂組合物1之製備
將3.44質量份之上述所獲得之色材分散液1、3.50質量份之感光性黏合劑成分B1、3.06質量份之PGMEA混合,製備實施例1之感光性著色樹脂組合物。
(2) Preparation of photosensitive adhesive component B1
Add 26.5 parts by mass of the alkali-soluble resin P1 solution (
(實施例2~27:感光性著色樹脂組合物2~27之製造) 於實施例1中,如表2所示般製備各感光性黏合劑成分B2~B27並使用,代替感光性黏合劑成分B1,除此以外,以與實施例1之感光性著色樹脂組合物1同樣之方式,獲得感光性著色樹脂組合物2~27。 (Examples 2-27: Production of Photosensitive Colored Resin Compositions 2-27) In Example 1, each photosensitive adhesive component B2 to B27 was prepared and used as shown in Table 2, instead of the photosensitive adhesive component B1. In the same manner, photosensitive colored resin compositions 2-27 were obtained.
(實施例28:感光性著色樹脂組合物28之製造)
於實施例2中,將色材分散液1中之色材自合成例1之三芳基甲烷系色澱色材1變更為合成例2之三芳基甲烷系色澱色材2,除此以外,以與實施例2同樣之方式,獲得感光性著色樹脂組合物28。
(Example 28: Production of Photosensitive Colored Resin Composition 28)
In Example 2, the color material in the
(比較例1~5:比較感光性著色樹脂組合物1~5之製造) 於實施例1中,如表3所示般製備各感光性黏合劑成分CB1~CB5並使用,代替感光性黏合劑成分B1,除此以外,以與實施例1之感光性著色樹脂組合物1同樣之方式,獲得比較感光性著色樹脂組合物1~5。 (Comparative Examples 1-5: Production of Comparative Photosensitive Colored Resin Compositions 1-5) In Example 1, each photosensitive adhesive component CB1 to CB5 was prepared and used as shown in Table 3, instead of the photosensitive adhesive component B1. In the same manner, Comparative Photosensitive Colored Resin Compositions 1-5 were obtained.
(比較例6~8:比較感光性著色樹脂組合物6~8之製造)
(1)色材分散液C1之製備
於225 mL蛋黃醬瓶中裝入PGMEA 65質量份、製備例1之鹼可溶性樹脂P1溶液(固形物成分40質量%)15質量份、合成例4之酸性分散劑A2之PGMEA溶液(固形物成分20.0質量%)10質量份並加以攪拌。
向其中裝入8.8質量份之PB15:6、1.2質量份之PV23、100質量份之粒徑2.0 mm之氧化鋯珠,利用塗料振盪機(淺田鐵工公司製造)振盪1小時作為預碎解,繼而變更為粒徑0.1 mm之氧化鋯珠200份,利用塗料振盪機進行4小時分散作為正式碎解,而獲得色材分散液C1。
(2)比較感光性著色樹脂組合物6~8之製備
於實施例1中,如表3所示般製備各感光性黏合劑成分CB6~CB8代替感光性黏合劑成分B1。
將2.56質量份之色材分散液C1、3.58質量份之感光性黏合劑成分、3.85質量份之PGMEA混合,而獲得比較感光性著色樹脂組合物6~8。
(Comparative Examples 6-8: Production of Comparative Photosensitive Colored Resin Compositions 6-8)
(1) Preparation of color material dispersion C1
In a 225 mL mayonnaise bottle, pack 65 mass parts of PGMEA, 15 mass parts of the alkali-soluble resin P1 solution (
(比較例9~11:比較感光性著色樹脂組合物9~11之製造)
於實施例1中,如表3所示般製備各感光性黏合劑成分CB9~CB11代替感光性黏合劑成分B1。
將染料(比較合成例1之三芳基甲烷系染料1)0.333質量份、感光性黏合劑成分4.17質量份、PGME 5.50質量份混合,而獲得比較感光性著色樹脂組合物9~11。
(Comparative Examples 9-11: Production of Comparative Photosensitive Colored Resin Compositions 9-11)
In Example 1, each photosensitive adhesive component CB9-CB11 was prepared as shown in Table 3 instead of the photosensitive adhesive component B1.
Comparative photosensitive colored resin compositions 9 to 11 were obtained by mixing 0.333 parts by mass of the dye (
[評價方法] 使用旋轉塗佈機,以後烘烤後之膜厚成為2.2 μm之方式,將實施例及比較例之感光性著色樹脂組合物分別塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS製造,「NA35」)上後,使用加熱板於80℃加熱乾燥3分鐘。其後,介隔形成40 μm之線之光罩,使用超高壓水銀燈照射60 mJ/cm 2之紫外線,繼而使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液,噴淋顯影60秒。其後,於230℃之潔淨烘箱中後烘烤30分鐘,藉此製作以40 μm之線之圖案於玻璃基板上形成有著色層之圖案形成基板。 [Evaluation method] Using a spin coater, the photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates (NH TECHNO GLASS Manufacture, "NA35"), heat and dry at 80°C for 3 minutes using a hot plate. Afterwards, irradiate ultraviolet rays of 60 mJ/cm 2 with an ultra-high pressure mercury lamp through a photomask forming a 40 μm line, and then use 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer to spray and develop for 60 seconds. Thereafter, it was post-baked in a clean oven at 230° C. for 30 minutes, thereby fabricating a pattern forming substrate in which a colored layer was formed on a glass substrate in a line pattern of 40 μm.
<著色層之線寬增加抑制> 利用光學顯微鏡對曝光時所使用之鉻遮罩之相當於開口寬度40 μm的部分之著色層之細線圖案之寬度測定5處,根據線寬之平均值與目標線寬之差評價線寬偏移量。 (線寬增加抑制評價基準) AA:相對於目標線寬,差為5.0 μm以內; A:相對於目標線寬,差超過5.0 μm且為7.0 μm以內; B:相對於目標線寬,差超過7.0 μm且為10.0 μm以內; C:相對於目標線寬,差超過10.0 μm。 若評價結果為A,則線寬增加抑制良好,若評價結果為AA,則線寬增加抑制優異。 <Inhibition of Line Width Increase in Colored Layer> Measure the width of the thin line pattern of the coloring layer in the chrome mask used for exposure with an optical microscope at a portion corresponding to an opening width of 40 μm, and evaluate the line width deviation based on the difference between the average line width and the target line width quantity. (Evaluation Criteria for Line Width Increase Suppression) AA: Relative to the target line width, the difference is within 5.0 μm; A: Relative to the target line width, the difference exceeds 5.0 μm and is within 7.0 μm; B: Relative to the target line width, the difference exceeds 7.0 μm and is within 10.0 μm; C: The difference exceeds 10.0 μm with respect to the target line width. If the evaluation result is A, the line width increase suppression is good, and if the evaluation result is AA, the line width increase suppression is excellent.
<顯影殘膜率評價> 以後烘烤後之膜厚成為2.2 μm之方式,使用旋轉塗佈機,將實施例及比較例之感光性著色樹脂組合物分別塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS製造,「NA35」)上後,使用加熱板於80℃加熱乾燥3分鐘。其後,不介隔光罩,使用超高壓水銀燈照射60 mJ/cm 2之紫外線,其後,使用膜厚計測定抗蝕劑塗膜之膜厚T1。繼而,使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液噴淋顯影60秒,測定顯影後之膜厚T2。 以顯影殘膜率=T2/T1[%]之形式算出。 (顯影殘膜率評價基準) AA:顯影殘膜率為98%以上; A:顯影殘膜率為97%以上且未達98%; B:顯影殘膜率為94%以上且未達97%; C:顯影殘膜率未達94%。 若評價結果為A,則顯影殘膜率良好,若評價結果為AA,則顯影殘膜率優異。 <Evaluation of developing residual film ratio> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates with a thickness of 0.7 mm using a spin coater so that the film thickness after baking was 2.2 μm ( Made by NH TECHNO GLASS, "NA35"), heat and dry at 80°C for 3 minutes using a hot plate. Thereafter, without intervening a photomask, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60 mJ/cm 2 , and thereafter, a film thickness T1 of the resist coating film was measured using a film thickness gauge. Next, spray image development was performed for 60 seconds using 0.05 mass % potassium hydroxide aqueous solution as an alkaline developing solution, and the film thickness T2 after image development was measured. It is calculated in the form of developing residual film rate=T2/T1[%]. (Evaluation criteria for developing residual film rate) AA: Developing residual film rate is above 98%; A: Developing residual film rate is above 97% and less than 98%; B: Developing residual film rate is above 94% and less than 97% ; C: The rate of remaining film after development does not reach 94%. If the evaluation result is A, the residual image development rate is good, and if the evaluation result is AA, the residual image development rate is excellent.
<亮度、耐熱性評價>
以後烘烤後之色度成為y=0.088之方式,使用旋轉塗佈機將實施例及比較例之感光性著色樹脂組合物分別塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS製造,「NA35」)上。其後,於80℃之加熱板上加熱乾燥3分鐘,不介隔光罩,使用超高壓水銀燈照射60 mJ/cm
2之紫外線,繼而於230℃之潔淨烘箱中後烘烤30分鐘,藉此獲得硬化膜(著色膜)。使用Olympus公司製造之「顯微分光測定裝置OSP-SP200」測定所獲得之著色基板之亮度(Y)、L、a、b(L
0、a
0、b
0),根據下述評價基準進行評價。
繼而,將上述形成有硬化膜之基板於230℃之潔淨烘箱中後烘烤30分鐘後,放置冷卻30分鐘,將上述步驟重複進行3次,測定所獲得之著色基板之L、a、b(L
1、a
1,b
1)。根據所測得之值,依據下述式算出處理前後之色差(ΔEab)。
色差(ΔEab)={(L
1-L
0)
2+(a
1-a
0)
2+(b
1-b
0)
2}
1/2 <Evaluation of Brightness and Heat Resistance> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on glass substrates with a thickness of 0.7 mm ( Made by NH TECHNO GLASS, "NA35"). Afterwards, heat and dry on a heating plate at 80°C for 3 minutes, and use an ultra-high pressure mercury lamp to irradiate ultraviolet rays of 60 mJ/cm 2 without intervening a light shield, and then bake in a clean oven at 230°C for 30 minutes, thereby A cured film (colored film) was obtained. The luminance (Y), L, a, b (L 0 , a 0 , b 0 ) of the obtained colored substrate was measured using the "microspectrometry device OSP-SP200" manufactured by Olympus Corporation, and evaluated according to the following evaluation criteria . Then, after baking the substrate with the above-mentioned cured film in a clean oven at 230° C. for 30 minutes, let it cool for 30 minutes, repeat the
(亮度評價基準) AA:亮度(Y)為10.6以上; A:亮度(Y)為10.0以上且未達10.6; B:亮度(Y)為9.5以上且未達10.0; C:亮度(Y)未達9.5。 若評價結果為A,則亮度良好,若評價結果為AA,則亮度優異。 (Brightness evaluation standard) AA: Brightness (Y) is above 10.6; A: Brightness (Y) is above 10.0 and less than 10.6; B: Brightness (Y) is above 9.5 and less than 10.0; C: Brightness (Y) is less than 9.5. If the evaluation result is A, the luminance is good, and if the evaluation result is AA, the luminance is excellent.
(耐熱性評價基準) AA:ΔEab未達3.0; A:ΔEab為3.0以上且未達5.0; B:ΔEab為5.0以上且未達8.0; C:ΔEab為8.0以上。 若評價結果為A,則耐熱性良好,若評價結果為AA,則耐熱性優異。 (Heat resistance evaluation standard) AA: ΔEab is less than 3.0; A: ΔEab is 3.0 or more and less than 5.0; B: ΔEab is 5.0 or more and less than 8.0; C: ΔEab is 8.0 or more. When the evaluation result is A, the heat resistance is good, and when the evaluation result is AA, the heat resistance is excellent.
[表2]
表2.
[表3]
表3.
於表中,簡稱如以下所述。 光起始劑1(I1):Irgacure 907,BASF製造,α-胺基苯乙酮系光起始劑 光起始劑2(I2):OXE-02,BASF製造,具有咔唑骨架之肟酯系光起始劑 紫外線吸收劑(U1):Kemisorb71,Chemipro Kasei製造 紫外線吸收劑(U2):Kemisorb12,Chemipro Kasei製造 紫外線吸收劑(U3):Kemisorb111,Chemipro Kasei製造 紫外線吸收劑(U4):Kemisorb73,Chemipro Kasei製造 紫外線吸收劑(U5):TinuvinPS,BASF製造 紫外線吸收劑(U6):Tinuvin928,BASF製造 紫外線吸收劑(U7):Tinuvin405,BASF製造 紫外線吸收劑(U8):Tinuvin479,BASF製造 紫外線吸收劑(U9):Tinuvin329,BASF製造 紫外線吸收劑(U10):Tinuvin477,BASF製造 紫外線吸收劑(U11):RUVA-93,大塚化學製造 抗氧化劑(A1):IRGANOX1010,BASF製造 潛在性抗氧化劑(LA1):合成例5之潛在性抗氧化劑 樹脂P1:製備例1之鹼可溶性樹脂P1 M1:光聚合性化合物,ARONIX M-403,二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯,東亞合成製造 M2:光聚合性化合物,ARONIX M-305,季戊四醇三丙烯酸酯及季戊四醇四丙烯酸酯,東亞合成製造 M3:光聚合性化合物,ARONIX M-460,二甘油環氧乙烷改性丙烯酸酯,東亞合成製造 M4:光聚合性化合物,Kayarad DPEA-12,環氧乙烷改性(12)二季戊四醇六丙烯酸酯,日本化藥製造 硫醇:Karenz MT PE1,昭和電工製造 In the table, the abbreviations are as follows. Photoinitiator 1 (I1): Irgacure 907, manufactured by BASF, α-aminoacetophenone-based photoinitiator Photoinitiator 2 (I2): OXE-02, manufactured by BASF, an oxime ester photoinitiator having a carbazole skeleton Ultraviolet absorber (U1): Kemisorb71, manufactured by Chemipro Kasei Ultraviolet absorber (U2): Kemisorb 12, manufactured by Chemipro Kasei Ultraviolet absorber (U3): Kemisorb 111, manufactured by Chemipro Kasei Ultraviolet absorber (U4): Kemisorb73, manufactured by Chemipro Kasei Ultraviolet absorber (U5): TinuvinPS, product made in BASF Ultraviolet absorber (U6): Tinuvin928, made by BASF Ultraviolet absorber (U7): Tinuvin405, made by BASF Ultraviolet absorber (U8): Tinuvin479, made by BASF Ultraviolet absorber (U9): Tinuvin329, made by BASF Ultraviolet absorber (U10): Tinuvin477, made by BASF Ultraviolet absorber (U11): RUVA-93, made by Otsuka Chemical Antioxidant (A1): IRGANOX1010, manufactured by BASF Potential antioxidant (LA1): potential antioxidant in Synthesis Example 5 Resin P1: Alkali-soluble resin P1 of Preparation Example 1 M1: Photopolymerizable compound, ARONIX M-403, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei M2: Photopolymerizable compound, ARONIX M-305, pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Toa Gosei M3: Photopolymerizable compound, ARONIX M-460, diglycerol ethylene oxide modified acrylate, manufactured by Toa Gosei M4: Photopolymerizable compound, Kayarad DPEA-12, ethylene oxide modified (12) dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Mercaptan: Karenz MT PE1, manufactured by Showa Denko
[表4]
[表5]
再者,光起始劑、紫外線吸收劑、抗氧化劑及硫醇之數值為固形物成分比。
L1(色澱色材1):合成例1之三芳基甲烷系染料之色澱色材1
L2(色澱色材2):合成例2之三芳基甲烷系染料之色澱色材2
顏料:PB15:6(C.I.顏料藍15:6)及PV23(C.I.顏料紫23)
染料:比較合成例1之三芳基甲烷系染料1
Furthermore, the numerical values of photoinitiator, ultraviolet absorber, antioxidant and mercaptan are solid content ratios.
L1 (color lake material 1): the
[結果總結] 將三芳基甲烷系染料之色澱色材與紫外線吸收劑組合之實施例1~28之感光性著色樹脂組合物能夠形成提高亮度並且藉由較細之線寬抑制顯影前後之膜厚變化之著色層。 又,於實施例中,若將三芳基甲烷系染料之色澱色材與紫外線吸收劑併用,則能夠於維持顯影殘膜率之狀態下,利用起始劑量將線寬偏移量調整為5 μm以下之目標值。 又,於實施例中,若使用於0.002質量%丙二醇單甲醚乙酸酯溶液中之波長365 nm下之透過率為40%以下之紫外線吸收劑,則不易使線寬偏移量增大。 又,於實施例中,於含有包含環氧烷之光聚合性化合物之情形時,容易兼顧較高之顯影殘膜率與較細之線寬。 與此相對,於不含紫外線吸收劑之比較例1之感光性著色樹脂組合物中,即便與實施例同樣地包含抗氧化劑及潛在性抗氧化劑,線寬偏移量亦較大,線寬亦變粗,而無法以所需之較細之線寬形成著色層。 於不含紫外線吸收劑之比較例1之感光性著色樹脂組合物中,於為了使線寬變細而減少了光起始劑量之比較例2及3之感光性著色樹脂組合物中,雖然線寬偏移量減少若干,但顯影殘膜率惡化。 於不含紫外線吸收劑之比較例1之感光性著色樹脂組合物中,於為了使線寬變細而增加了抗氧化劑量之比較例4及5之感光性著色樹脂組合物中,雖然線寬偏移量減少,但顯影殘膜率惡化。 另一方面,於不使用三芳基甲烷系染料之色澱色材而使用顏料之比較例6~8之感光性著色樹脂組合物中,為了設為與使用三芳基甲烷系染料之色澱色材之實施例同樣之線寬偏移量,需要大量使用光起始劑量,於該情形時,顯影殘膜率不成為問題,但亮度較低。 又,於不使用三芳基甲烷系染料之色澱色材而使用三芳基甲烷系染料之比較例9~11之感光性著色樹脂組合物中,為了設為與使用三芳基甲烷系染料之色澱色材之實施例同樣之線寬偏移量,需要大量使用光起始劑量,於該情形時,顯影殘膜率不成為問題,但加熱後之色差增大,亮度降低。 [Summary of results] The photosensitive coloring resin compositions of Examples 1 to 28 in which a triarylmethane-based dye lake coloring material is combined with an ultraviolet absorber can form coloring that improves brightness and suppresses changes in film thickness before and after development with thinner line widths layer. Also, in the embodiment, if the color lake material of the triarylmethane series dye is used together with the ultraviolet absorber, the line width deviation can be adjusted to 5 by using the starting dose while maintaining the residual film rate of development. The target value below μm. Also, in the examples, if an ultraviolet absorber having a transmittance of 40% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution is used, it is difficult to increase the amount of line width shift. Moreover, in an Example, when containing the photopolymerizable compound containing an alkylene oxide, it becomes easy to make both a high developing residual film rate and a narrow line width compatible. On the other hand, in the photosensitive colored resin composition of Comparative Example 1 that does not contain an ultraviolet absorber, even though antioxidants and latent antioxidants are included in the same manner as in Examples, the line width deviation is large, and the line width is also large. becomes thicker, and cannot form a colored layer with the required thinner line width. In the photosensitive colored resin composition of Comparative Example 1 that does not contain an ultraviolet absorber, in the photosensitive colored resin compositions of Comparative Examples 2 and 3 in which the amount of photoinitiator was reduced in order to make the line width thinner, although the line The amount of wide offset decreased somewhat, but the residual film rate deteriorated. In the photosensitive colored resin composition of Comparative Example 1 that did not contain an ultraviolet absorber, in the photosensitive colored resin compositions of Comparative Examples 4 and 5 in which the amount of antioxidant was increased to make the line width thinner, although the line width The amount of offset decreased, but the residual film rate deteriorated. On the other hand, in the photosensitive colored resin compositions of Comparative Examples 6 to 8 in which a pigment was used without using a triarylmethane-based dye lake material, in order to be compatible with the lake color material using a triarylmethane-based dye The same line width offset in the above embodiment requires a large amount of photoinitial dose. In this case, the residual film rate is not a problem, but the brightness is low. In addition, in the photosensitive colored resin compositions of Comparative Examples 9 to 11 in which a triarylmethane-based dye was used without using a triarylmethane-based dye lake color material, in order to set it as a color lake using a triarylmethane-based dye The same line width offset in the embodiment of the color material requires a large amount of photoinitiator dose. In this case, the residual film rate of development is not a problem, but the color difference after heating increases and the brightness decreases.
1:基板 2:遮光部 3:著色層 5:微小孔 10:彩色濾光片 20:對向基板 30:液晶層 40:液晶顯示裝置 50:有機保護層 60:無機氧化膜 71:透明陽極 72:電洞注入層 73:電洞傳輸層 74:發光層 75:電子注入層 76:陰極 80:有機發光體 100:有機發光顯示裝置 1: Substrate 2: shading part 3: coloring layer 5: tiny hole 10:Color filter 20: facing the substrate 30: Liquid crystal layer 40: Liquid crystal display device 50: organic protective layer 60: Inorganic oxide film 71: Transparent anode 72: Hole injection layer 73: Hole transport layer 74: luminous layer 75: Electron injection layer 76: Cathode 80: organic luminous body 100: Organic light-emitting display device
圖1係表示本發明之彩色濾光片之一例的概略圖。 圖2係表示本發明之液晶顯示裝置之一例的概略圖。 圖3係表示本發明之有機發光顯示裝置之一例的概略圖。Fig. 1 is a schematic diagram showing an example of the color filter of the present invention. Fig. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of an organic light-emitting display device of the present invention.
1:基板 1: Substrate
2:遮光部 2: shading part
3:著色層 3: coloring layer
10:彩色濾光片 10:Color filter
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