TW202219192A - Photosensitive colored resin composition for color filter, cured product, color filter and display device - Google Patents

Photosensitive colored resin composition for color filter, cured product, color filter and display device Download PDF

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TW202219192A
TW202219192A TW110128859A TW110128859A TW202219192A TW 202219192 A TW202219192 A TW 202219192A TW 110128859 A TW110128859 A TW 110128859A TW 110128859 A TW110128859 A TW 110128859A TW 202219192 A TW202219192 A TW 202219192A
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大島裕史
田尻亘
境美嘉
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日商Dnp精細化工股份有限公司
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
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    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

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Abstract

A photosensitive colored resin composition for color filter, comprising a color material, a binder resin, a monomer, a photoinitiator and a solvent, wherein the color material contains at least one selected from the group consisting of a dye and a lake color material, and wherein the binder resin contains a copolymer which includes a polymeric structure such that a constitutional unit represented by the following general formula (A) and derived from hydroxyalkyl (meth)acrylate is contained in an amount of 5 mass % to 25 mass %, which has a weight average molecular weight of 11000 or more, and which has an acid value of 60 mgKOH/g to 130 mgKOH/g: (where R<SP>A</SP> is a methyl group or a hydrogen atom, and R<SP>B</SP> is an alkylene group containing 1 to 4 carbon atoms.).

Description

彩色濾光片用感光性著色樹脂組合物、硬化物、彩色濾光片、及顯示裝置Photosensitive colored resin composition for color filter, cured product, color filter, and display device

本發明係關於一種彩色濾光片用感光性著色樹脂組合物及其硬化物、彩色濾光片、以及顯示裝置。The present invention relates to a photosensitive colored resin composition for a color filter, a cured product thereof, a color filter, and a display device.

近年來,隨著個人電腦之進步、尤其是攜帶用個人電腦之進步,液晶顯示器之需求正在不斷增加。行動顯示器(行動電話、智慧型手機、平板PC(Personal Computer,個人電腦))之普及率亦越來越高,液晶顯示器之市場正在逐漸擴大。又,最近,因自發光而具高視認性之如有機EL(Electroluminescence,電致發光)顯示器之有機發光顯示裝置,亦作為下一代影像顯示裝置而備受關注。對於該等影像顯示裝置之性能,人們強烈期望對比度或顏色再現性之提高等進一步之高畫質化、及耗電之降低。In recent years, with the advancement of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs (Personal Computer)) is also increasing, and the market for liquid crystal displays is gradually expanding. In addition, recently, organic light-emitting display devices such as organic EL (Electroluminescence) displays, which have high visibility due to self-luminescence, are also attracting attention as next-generation image display devices. With regard to the performance of these image display devices, further improvement in image quality, such as improvement in contrast ratio and color reproducibility, and reduction in power consumption are strongly desired.

該等液晶顯示裝置及有機發光顯示裝置中使用彩色濾光片。例如於形成液晶顯示裝置之彩色影像時,穿過彩色濾光片之光直接被著色成構成彩色濾光片之各像素之顏色,該等顏色之光被合成而形成彩色影像。作為此時之光源,除使用先前之冷陰極管以外,有時還使用發白色光之有機發光元件或發白色光之無機發光元件。又,於有機發光顯示裝置中,為了調整顏色等而使用彩色濾光片。 於此種狀況下,對於彩色濾光片亦同樣地要求高亮度化及高對比度化、顏色再現性之提高等。 Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image of a liquid crystal display device, 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 the light source at this time, in addition to the conventional cold cathode tube, an organic light-emitting element that emits white light or an inorganic light-emitting element that emits white light is sometimes used. In addition, in organic light-emitting display devices, color filters are used for color adjustment and the like. Under such circumstances, the color filter is also required to have high brightness, high contrast, improvement of color reproducibility, and the like.

此處,彩色濾光片一般具有:透明基板;著色層,其形成於透明基板上且包含紅、綠、藍三原色之著色圖案;及遮光部,其以劃分各著色圖案之方式形成於透明基板上。 作為彩色濾光片中之著色層之形成方法,例如按照以下方式形成,即,向利用分散劑等使色料分散而成之色料分散液中添加黏合劑樹脂、光聚合性化合物及光起始劑而形成感光性著色樹脂組合物,將該感光性著色樹脂組合物塗佈於玻璃基板並進行乾燥後,使用光罩進行曝光,進行顯影,藉此形成著色圖案,藉由加熱而將圖案加以固定,從而形成著色層。針對各個顏色重複進行該等步驟,而形成彩色濾光片。 Here, a color filter generally has: a transparent substrate; a colored layer formed on the transparent substrate and including colored patterns of three primary colors of red, green, and blue; and a light-shielding portion formed on the transparent substrate by dividing the colored patterns superior. As a method for forming a coloring layer in a color filter, for example, it is formed by adding a binder resin, a photopolymerizable compound, and a photopolymer to a colorant dispersion liquid obtained by dispersing a colorant with a dispersant or the like. A photosensitive coloring resin composition is formed by using a starting agent, the photosensitive coloring resin composition is applied to a glass substrate and dried, then exposed using a mask and developed to form a colored pattern, and the pattern is formed by heating. fixed to form a colored layer. These steps are repeated for each color to form a color filter.

對於彩色濾光片形成用感光性著色樹脂組合物,要求具有能夠準確地形成著色層之優異之顯影性。 專利文獻1中提出了一種彩色濾光片用著色感光性樹脂組合物,其含有顏料、黏合劑樹脂、多官能性單體、光起始劑、分散劑、及溶劑,且上述黏合劑樹脂包含具有下述主鏈結構之共聚物,該主鏈結構係至少由具有烷基環己基之(甲基)丙烯酸烷基環己酯、及具有酸基之單體共聚而成,上述共聚物之羥值處於15 mgKOH/g~200 mgKOH/g之範圍內。 據專利文獻1中記載,該著色感光性樹脂組合物之未曝光部位之顯影殘渣較少,曝光部位之殘膜率較高。 The photosensitive coloring resin composition for color filter formation is required to have excellent developability which can form a coloring layer accurately. Patent Document 1 proposes a colored photosensitive resin composition for a color filter, which contains a pigment, a binder resin, a polyfunctional monomer, a photoinitiator, a dispersant, and a solvent, and the binder resin contains A copolymer having the following main chain structure, the main chain structure is at least copolymerized from alkyl cyclohexyl (meth)acrylate having an alkyl cyclohexyl group and a monomer having an acid group, and the hydroxyl group of the above-mentioned copolymer is copolymerized. The value is in the range of 15 mgKOH/g to 200 mgKOH/g. According to patent document 1, the unexposed part of this colored photosensitive resin composition has few development residues, and the residual film rate of an exposed part is high.

又,對於彩色濾光片形成用感光性著色樹脂組合物,要求能夠形成高亮度之著色層。因此,正在研究使用經微細化之顏料作為色料,或者使用染料或色澱色料作為透過率更高之色料。 先前技術文獻 專利文獻 Moreover, about the photosensitive coloring resin composition for color filter formation, the coloring layer which can form a high brightness is calculated|required. Therefore, studies are underway to use micronized pigments as colorants, or to use dyes or lake colorants as colorants with higher transmittance. prior art literature Patent Literature

專利文獻1:日本專利特開2009-276674號公報Patent Document 1: Japanese Patent Laid-Open No. 2009-276674

[發明所欲解決之問題][Problems to be Solved by Invention]

為了提高彩色濾光片之亮度,本發明人等嘗試了使用染料或色澱色料作為感光性著色樹脂組合物之色料。然而,於使用含有染料或色澱色料之感光性著色樹脂組合物來形成由紅、綠、藍等2色以上之著色層呈規定圖案狀排列而成之著色層圖案時,已判明像素內膜厚分佈變得不均勻,像素之平坦性受損。 本發明係鑒於上述實際情況而完成者,其目的在於提供一種彩色濾光片用感光性著色樹脂組合物,其藉由含有選自染料及色澱色料中之至少一種色料,而能夠形成高亮度,並且平坦性優異,顯影殘渣之產生得到抑制之著色層。又,本發明之目的在於提供一種該感光性著色樹脂組合物之硬化物、以及使用該感光性著色樹脂組合物而形成之彩色濾光片及顯示裝置。 [解決問題之技術手段] In order to improve the brightness of the color filter, the inventors of the present invention tried to use dyes or lake colorants as the colorant of the photosensitive coloring resin composition. However, when a photosensitive coloring resin composition containing a dye or lake colorant is used to form a coloring layer pattern in which two or more coloring layers such as red, green, and blue are arranged in a predetermined pattern, it has been found that in the pixel The film thickness distribution becomes non-uniform, and the flatness of the pixels is impaired. The present invention has been made in view of the above-mentioned circumstances, and its object is to provide a photosensitive colored resin composition for color filters, which can be formed by containing at least one colorant selected from dyes and lake colorants. A coloring layer with high brightness, excellent flatness, and suppressed development residues. Moreover, the objective of this invention is to provide the hardened|cured material of this photosensitive coloring resin composition, and the color filter and display apparatus formed using this photosensitive coloring resin composition. [Technical means to solve problems]

本發明之彩色濾光片用感光性著色樹脂組合物係含有色料、黏合劑樹脂、單體、光起始劑、及溶劑者,且  上述色料包含選自由染料及色澱色料所組成之群中之至少一種,  上述黏合劑樹脂包含下述共聚物,該共聚物具有包含5~25質量%之下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元的高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g。The photosensitive colored resin composition for color filters of the present invention contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, and the colorant is selected from the group consisting of dyes and lake colorants At least one of the group, the above-mentioned binder resin contains the following copolymer, and the copolymer has 5-25 mass % of the hydroxyalkyl (meth)acrylate-derived compound represented by the following general formula (A). The polymer structure of the structural unit, the weight average molecular weight is 11000 or more, and the acid value is 60-130 mgKOH/g.

[化1]  通式(A)

Figure 02_image005
(通式(A)中,R A表示甲基或氫原子,R B表示碳數1~4之伸烷基) [Chemical 1] General formula (A)
Figure 02_image005
(In the general formula (A), R A represents a methyl group or a hydrogen atom, and R B represents an alkylene group having 1 to 4 carbon atoms)

本發明提供一種硬化物,其係上述本發明之彩色濾光片用感光性著色樹脂組合物之硬化物。 本發明提供一種彩色濾光片,其至少具備基板、及設置於該基板上之著色層,且該著色層之至少1個為上述本發明之彩色濾光片用感光性著色樹脂組合物之硬化物。 The present invention provides a cured product which is a cured product of the photosensitive colored resin composition for color filters of the present invention. The present invention provides a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is cured of the photosensitive colored resin composition for a color filter of the present invention. thing.

本發明提供一種顯示裝置,其具有上述本發明之彩色濾光片。 [發明之效果] The present invention provides a display device having the above-mentioned color filter of the present invention. [Effect of invention]

根據本發明,可提供一彩色濾光片用感光性著色樹脂組合物,其藉由含有選自染料及色澱色料中之至少一種色料,而能夠形成高亮度,並且平坦性優異,顯影殘渣之產生得到抑制之著色層。又,根據本發明,可提供一種該感光性著色樹脂組合物之硬化物、以及使用該感光性著色樹脂組合物而形成之彩色濾光片及顯示裝置。According to the present invention, a photosensitive colored resin composition for a color filter can be provided, which can form high brightness by containing at least one colorant selected from dyes and lake colorants, has excellent flatness, and can be developed A colored layer in which the generation of residues is suppressed. Moreover, according to this invention, the hardened|cured material of this photosensitive coloring resin composition, and the color filter and display apparatus formed using this photosensitive coloring resin composition can be provided.

以下,依序對本發明之彩色濾光片用感光性著色樹脂組合物及其製造方法、以及本發明之彩色濾光片用感光性著色樹脂組合物之硬化物、使用本發明之彩色濾光片用感光性著色樹脂組合物而形成之彩色濾光片及顯示裝置進行詳細說明。  再者,於本發明中,光包含可見及不可見區域之波長之電磁波、以及輻射,輻射例如包含微波、電子束。具體而言,意指波長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各者,(甲基)丙烯酸表示丙烯酸及甲基丙烯酸各者,(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯各者。 又,於本說明書中,表示數值範圍之「~」係以將其前後所記載之數值作為下限值及上限值而包含之含義使用。 於本發明中,固形物成分係指感光性著色樹脂組合物中所含有之成分中除溶劑以外之全部,亦包含單體等液狀成分。 Hereinafter, the photosensitive colored resin composition for color filters of the present invention, a method for producing the same, and the cured product of the photosensitive colored resin composition for color filters of the present invention, the color filters of the present invention are used in this order. The color filter and display apparatus formed using the photosensitive coloring resin composition are demonstrated in detail. Furthermore, in the present invention, light includes electromagnetic waves of wavelengths in the visible and invisible regions, and radiation, such as radiation including microwaves and electron beams. Specifically, it means an electromagnetic wave with a wavelength of 5 μm or less and an electron beam. In the present invention, (meth)acryloyl group represents each of acryl group and methacryloyl group, (meth)acrylic acid represents each of acrylic acid and methacrylic acid, and (meth)acrylate represents acrylate and methyl ester. based on acrylates. In addition, in this specification, "-" which shows a numerical range is used in the meaning including the numerical value described before and after it as a lower limit and an upper limit. In the present invention, the solid content refers to all of the components contained in the photosensitive colored resin composition except for the solvent, and also includes liquid components such as monomers.

I.彩色濾光片用感光性著色樹脂組合物 本發明之彩色濾光片用感光性著色樹脂組合物(以下,有時稱為「感光性著色樹脂組合物」)係含有色料、黏合劑樹脂、單體、光起始劑、及溶劑者,且 上述色料包含選自由染料及色澱色料所組成之群中之至少一種,  上述黏合劑樹脂包含下述共聚物,該共聚物具有包含5~25質量%之下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元的高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g。 I. Photosensitive Colored Resin Composition for Color Filters The photosensitive colored resin composition for color filters of the present invention (hereinafter, sometimes referred to as "photosensitive colored resin composition") contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent ,and The above-mentioned colorant includes at least one selected from the group consisting of dyes and lake colorants, and the above-mentioned binder resin includes the following copolymer, and the copolymer has the following general formula (A) in an amount of 5-25% by mass. It represents the polymer structure derived from the structural unit of hydroxyalkyl (meth)acrylate, and has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH/g.

本發明之感光性著色樹脂組合物含有選自由染料及色澱色料所組成之群中之至少一種作為色料。相較於顏料,染料及色澱色料之透過率較高,因此藉由使用選自由染料及色澱色料所組成之群中之至少一種作為感光性著色樹脂組合物之色料,可形成高亮度之著色層。 然而,將感光性著色樹脂組合物塗佈於基板上,呈規定圖案狀進行曝光,進行顯影而形成著色層,將此一連串之步驟以改變色料之顏色之方式依序在一個基板上進行,藉此形成由紅、綠、藍等2色以上之著色層呈規定圖案狀排列而成之著色層圖案,於上述著色層圖案之形成方法中,已判明當使用含有染料或色澱色料之感光性著色樹脂組合物時,第2個以後所形成之著色層之膜厚分佈變得不均勻,導致像素之平坦性受損。 像素內膜厚分佈之均勻性關係到像素內之色度均勻性,其係對於提高畫質而言較重要之要素。尤其是,若像素密度隨著顯示裝置之高解析度化而變高,則像素內膜厚分佈之均勻性對畫質產生之影響會越來越大。 像素之平坦性受損這一問題於使用染料或色澱色料作為感光性著色樹脂組合物之色料時尤其明顯。 The photosensitive colored resin composition of the present invention contains at least one selected from the group consisting of dyes and lake colorants as a colorant. Compared with pigments, dyes and lake colorants have higher transmittance, so by using at least one selected from the group consisting of dyes and lake colorants as the colorant of the photosensitive coloring resin composition, it is possible to form High brightness tinting layer. However, the photosensitive colored resin composition is coated on a substrate, exposed in a predetermined pattern, and developed to form a colored layer, and this series of steps are sequentially performed on one substrate by changing the color of the toner, In this way, a coloring layer pattern is formed in which coloring layers of two or more colors such as red, green, and blue are arranged in a predetermined pattern. In the above-mentioned method for forming the coloring layer pattern, it has been found that the use of dyes or lakes. In the case of the photosensitive coloring resin composition, the film thickness distribution of the coloring layer formed after the second becomes non-uniform, and the flatness of the pixel is impaired. The uniformity of the film thickness distribution in the pixel is related to the chromaticity uniformity in the pixel, which is an important factor for improving the image quality. In particular, if the pixel density becomes higher as the resolution of the display device becomes higher, the uniformity of the film thickness distribution in the pixel will have an increasing influence on the image quality. The problem that the flatness of the pixels is impaired is particularly noticeable when dyes or lake colorants are used as the colorant of the photosensitive coloring resin composition.

圖4係表示使用含有顏料之感光性著色樹脂組合物來形成彩色濾光片之著色層之習知方法之一例的概略圖。圖4表示於基板上依序形成紅色著色層3R及綠色著色層3G後,形成藍色著色層3B之步驟。圖4之4(a)示出了於設置有成為各著色層之交界之遮光部2、紅色著色層3R及綠色著色層3G之基板上,使用藍色之感光性著色樹脂組合物形成了藍色塗膜3B'之狀態。藍色塗膜3B'會追隨塗佈面之凹凸形狀,因此塗膜表面之高度於待形成藍色著色層之區域變得相對較低,於設置有紅色著色層3R及綠色著色層3G之區域變得相對較高。藍色塗膜3B'之厚度僅在待形成藍色著色層之區域內固定,其表面追隨基底之表面形狀而變得平坦。繼而,對該藍色塗膜3B'進行加熱乾燥。加熱乾燥後之藍色塗膜3B'如圖4之4(b)所示,維持著與加熱乾燥前相同之形狀。加熱乾燥後,將藍色塗膜3B'呈規定圖案狀進行曝光,選擇性地使待形成藍色著色層之區域硬化後,進行顯影,藉此如圖4之4(c)所示,形成平坦形狀之藍色著色層3B。4 is a schematic diagram showing an example of a conventional method for forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. FIG. 4 shows the step of forming the blue colored layer 3B after the red colored layer 3R and the green colored layer 3G are sequentially formed on the substrate. 4(a) of FIG. 4 shows that a blue photosensitive coloring resin composition is used to form a blue light-shielding portion 2, a red coloring layer 3R, and a green coloring layer 3G that serve as boundaries between the coloring layers. The state of the color coating film 3B'. The blue coating film 3B' will follow the uneven shape of the coating surface, so the height of the coating film surface becomes relatively lower in the area where the blue coloring layer is to be formed, and in the area where the red coloring layer 3R and the green coloring layer 3G are provided become relatively high. The thickness of the blue coating film 3B' is fixed only in the region where the blue colored layer is to be formed, and the surface thereof becomes flat following the surface shape of the substrate. Next, this blue coating film 3B' is heated and dried. As shown in FIG. 4(b), the blue coating film 3B' after heating and drying maintained the same shape as before heating and drying. After heating and drying, the blue coating film 3B' is exposed to light in a predetermined pattern, and the region where the blue colored layer is to be formed is selectively hardened, and then developed, as shown in FIG. 4(c) , to form a Flat-shaped blue colored layer 3B.

另一方面,圖5係表示使用含有染料或色澱色料之感光性著色樹脂組合物來形成彩色濾光片之著色層之習知方法之一例的概略圖。圖5表示於基板上依序形成紅色著色層3R及綠色著色層3G後,形成藍色著色層3B之步驟。圖5之5(a)示出了於設置有成為各著色層之交界之遮光部2、紅色著色層3R及綠色著色層3G之基板上,使用藍色之感光性著色樹脂組合物形成了藍色塗膜3B'之狀態。於該階段,含有染料或色澱色料之藍色塗膜3B'與圖4之4(a)之含有顏料之藍色塗膜3B'同樣地,塗膜表面之高度於待形成藍色著色層之區域變得相對較低,於設置有紅色著色層3R及綠色著色層3G之區域變得相對較高,藍色塗膜3B'之厚度僅在待形成藍色著色層之區域內固定,其表面追隨基底之表面形狀而變得平坦。再者,圖5之5(a)中所示之綠色著色層3G係於基板上第2個形成之著色層,與圖4之4(a)之含有顏料之綠色著色層3G不同,具有平坦性欠佳之形狀。關於該點將於下文進行說明。 繼而,當對該藍色塗膜3B'進行加熱乾燥時,藍色塗膜因加熱而流動,因此,如圖5之5(b)所示,藍色塗膜3B'中存在於設置有紅色著色層3R及綠色著色層3G之區域且塗膜表面之高度相對較高之部分,跨越設置有紅色著色層3R之區域與待形成藍色著色層之區域之交界、及設置有綠色著色層3G之區域與待形成藍色著色層之區域之交界,流入至存在於待形成藍色著色層之區域且塗膜表面之高度相對較低之部分。因此,加熱乾燥後之藍色塗膜3B'失去針對基底之表面形狀之追隨性,塗膜表面於設置有紅色著色層3R之區域與待形成藍色著色層之區域之交界附近、及設置有綠色著色層3G之區域與待形成藍色著色層之區域之交界附近變得相對較高,塗膜表面於中央部變得相對較低,整體上成為中央部凹陷之表面形狀。加熱乾燥後,將藍色塗膜呈規定圖案狀進行曝光,選擇性地使待形成藍色著色層之區域硬化後,進行顯影,藉此如圖5之5(c)所示,形成中央部凹陷之形狀之藍色著色層3B。 On the other hand, FIG. 5 is a schematic diagram showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a dye or a lake coloring material. FIG. 5 shows the step of forming the blue coloring layer 3B after the red coloring layer 3R and the green coloring layer 3G are sequentially formed on the substrate. 5(a) of FIG. 5 shows that a blue photosensitive coloring resin composition is used to form a blue light-shielding portion 2, a red coloring layer 3R, and a green coloring layer 3G that serve as boundaries between the coloring layers. The state of the color coating film 3B'. At this stage, the blue coating film 3B' containing dyes or lake colorants is the same as the blue coating film 3B' containing pigments in Fig. 4(a), and the height of the coating film surface is higher than the blue coloring to be formed. The area of the layer becomes relatively lower, the area where the red coloring layer 3R and the green coloring layer 3G are provided becomes relatively high, and the thickness of the blue coating film 3B' is fixed only in the area where the blue coloring layer is to be formed, Its surface becomes flat following the surface shape of the substrate. Furthermore, the green coloring layer 3G shown in FIG. 5(a) is the second coloring layer formed on the substrate, which is different from the green coloring layer 3G containing pigment in FIG. 4(a), and has a flat surface. Sexually inappropriate shape. This point will be explained below. Then, when the blue coating film 3B' is heated and dried, the blue coating film flows due to the heating. Therefore, as shown in FIG. The region of the coloring layer 3R and the green coloring layer 3G and the part with a relatively high height of the coating film surface spans the boundary between the region where the red coloring layer 3R is provided and the region where the blue coloring layer is to be formed, and the green coloring layer 3G is provided The boundary between the area where the blue coloring layer is to be formed and the area where the blue coloring layer is to be formed flows into the part that exists in the area where the blue coloring layer is to be formed and the height of the coating film surface is relatively low. Therefore, the blue coating film 3B' after heating and drying loses the followability to the surface shape of the substrate, and the coating film surface is located near the boundary between the region where the red coloring layer 3R is provided and the region where the blue coloring layer is to be formed, and the The vicinity of the boundary between the area of the green coloring layer 3G and the area where the blue coloring layer is to be formed becomes relatively high, and the coating film surface becomes relatively low in the central portion, and the overall surface shape is concave in the central portion. After heating and drying, the blue coating film is exposed to light in a predetermined pattern, and the region where the blue coloring layer is to be formed is selectively hardened and then developed, thereby forming the central portion as shown in FIG. 5(c) . The blue colored layer 3B in the shape of the depression.

於使用含有染料或色澱色料之感光性著色樹脂組合物在基板上形成第2個以後之著色層之情形時,感光性著色樹脂組合物之塗膜於加熱乾燥步驟中,與上文所述同樣地軟化、流動,失去針對基底之表面形狀之追隨性,因此容易形成下述形狀之著色層,該形狀係在與基板上先形成之著色層鄰接之交界附近塗膜表面相對較高。 例如,於使用含有染料或色澱色料之感光性著色樹脂組合物於基板上依序形成紅色著色層、綠色著色層及藍色著色層之情形時,綠色著色層如圖5之5(a)所示,容易形成為下述形狀,該形狀係與紅色著色層鄰接之交界部處之塗膜高度相對較高,且中央部及遠離紅色著色層之部分之塗膜高度相對較低。 When the second and subsequent colored layers are formed on the substrate using the photosensitive coloring resin composition containing dyes or lake colorants, the coating film of the photosensitive coloring resin composition is heated and dried in the same manner as described above. It softens and flows as described above, and loses the followability to the surface shape of the substrate, so it is easy to form a coloring layer of a shape that is relatively high on the surface of the coating film near the junction adjacent to the coloring layer formed earlier on the substrate. For example, when a photosensitive colored resin composition containing dyes or lake colorants is used to form a red colored layer, a green colored layer and a blue colored layer on the substrate in sequence, the green colored layer is shown in Fig. 5(a) ), it is easy to form a shape in which the height of the coating film at the boundary portion adjacent to the red coloring layer is relatively high, and the height of the coating film at the center portion and the portion far from the red coloring layer is relatively low.

對感光性著色樹脂組合物之塗膜進行加熱乾燥時之流動性會根據所使用之色料而有所不同,推測其原因在於:於使用顏料作為色料之情形時,顏料之微粒子分散於感光性著色樹脂組合物中,因此於加熱乾燥時,即便塗膜軟化,黏度亦未過於降低;相對於此,於使用染料或色澱色料作為色料之情形時,染料或色澱色料溶解於感光性著色樹脂組合物中,或者以較顏料粒子更微細化之狀態分散於感光性著色樹脂組合物中,因此於加熱乾燥時,若塗膜軟化,則黏度變低,而流動性變大。The fluidity of the coating film of the photosensitive colored resin composition when heated and dried varies depending on the colorant used, and the reason is presumed that when a pigment is used as the colorant, the fine particles of the pigment are dispersed in the photosensitive material. Therefore, when heating and drying, even if the coating film is softened, the viscosity will not decrease too much; in contrast, when dyes or lake colorants are used as colorants, the dyes or lake colorants are dissolved. In the photosensitive colored resin composition, or dispersed in the photosensitive colored resin composition in a state of being finer than the pigment particles, when the coating film is softened during heating and drying, the viscosity becomes lower and the fluidity becomes larger. .

於本發明中,藉由使用包含下述共聚物之黏合劑樹脂,可解決使用染料或色澱色料作為感光性著色樹脂組合物之色料時特有之上述問題,上述共聚物具有包含5~25質量%之下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元的高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g(以下,有時將該共聚物稱為「含有(甲基)丙烯酸羥烷基酯單元之共聚物」)。 於在含有染料或色澱色料之感光性著色樹脂組合物中使用包含含有(甲基)丙烯酸羥烷基酯單元之共聚物之黏合劑樹脂之情形時,對形成於基板上之感光性著色樹脂組合物之塗膜進行加熱乾燥時,流動性之增大得到抑制,因此,將感光性著色樹脂組合物塗佈於基板時,塗膜之平坦性在加熱乾燥後亦容易維持不變,而形成平坦性優異之形狀之著色層。 於使用上述包含含有(甲基)丙烯酸羥烷基酯單元之共聚物之黏合劑樹脂之情形時,會形成平坦性優異之形狀之著色層,其原因推測如下。 認為於對感光性著色樹脂組合物之塗膜進行加熱乾燥時,塗膜中之溶劑量減少而使黏合劑樹脂分子之分子間距離變小,氫鍵對黏合劑樹脂分子間之鍵結力之影響增大。上述含有(甲基)丙烯酸羥烷基酯單元之共聚物已將源自(甲基)丙烯酸羥烷基酯之結構單元之含量調節至適當之範圍內,因此,當對感光性著色樹脂組合物之塗膜進行加熱乾燥時,藉由黏合劑樹脂分子間之氫鍵受到含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥基促進之效果,而使已軟化之塗膜之黏度上升,從而可抑制塗膜之流動化。 又,上述含有(甲基)丙烯酸羥烷基酯單元之共聚物已將重量平均分子量調節至適當之範圍內,因此,認為當對感光性著色樹脂組合物之塗膜進行加熱乾燥時,藉由分子量效應而使已軟化之塗膜之黏度上升,從而可抑制塗膜之流動化。 作為抑制感光性著色樹脂組合物之塗膜軟化之其他方法,亦想到將熔融黏度較高之其他樹脂用作黏合劑樹脂之方法、或者將具有促進黏合劑樹脂內之氫鍵之其他官能基之樹脂用作黏合劑樹脂之方法,但上述含有(甲基)丙烯酸羥烷基酯單元之共聚物在以下方面優異,即,能夠以相對較少之量來有效地使著色層之形狀平坦化,且不會對著色層之色調產生不良影響。 In the present invention, the above-mentioned problems peculiar to the use of dyes or lake colorants as the colorant of the photosensitive coloring resin composition can be solved by using a binder resin containing the following copolymers, wherein the copolymers contain 5- 25% by mass of a polymer structure derived from a structural unit of hydroxyalkyl (meth)acrylate represented by the following general formula (A), with a weight average molecular weight of 11,000 or more, and an acid value of 60 to 130 mgKOH/g (Hereinafter, this copolymer may be referred to as a "copolymer containing a hydroxyalkyl (meth)acrylate unit"). In the case of using a binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit in a photosensitive coloring resin composition containing a dye or lake colorant, photosensitive coloring formed on a substrate When the coating film of the resin composition is heated and dried, the increase in fluidity is suppressed. Therefore, when the photosensitive colored resin composition is coated on the substrate, the flatness of the coating film is easily maintained after heating and drying. A colored layer with a shape excellent in flatness is formed. When the binder resin containing the copolymer containing the hydroxyalkyl (meth)acrylate unit mentioned above is used, the coloring layer of the shape excellent in flatness is formed, and the reason is presumed to be as follows. It is considered that when the coating film of the photosensitive coloring resin composition is heated and dried, the amount of solvent in the coating film decreases, so that the intermolecular distance between the molecules of the binder resin becomes smaller, and the hydrogen bond has an effect on the bonding force between the molecules of the binder resin. influence increases. The above-mentioned copolymers containing hydroxyalkyl (meth)acrylate units have adjusted the content of the structural units derived from hydroxyalkyl (meth)acrylates to an appropriate range. Therefore, when the photosensitive coloring resin composition is used When the coating film is heated and dried, the hydrogen bond between the binder resin molecules is promoted by the hydroxyl groups of the copolymer containing hydroxyalkyl (meth)acrylate units, so that the viscosity of the softened coating film increases, As a result, fluidization of the coating film can be suppressed. In addition, the weight average molecular weight of the above-mentioned copolymer containing hydroxyalkyl (meth)acrylate units has been adjusted to an appropriate range. Therefore, it is considered that when the coating film of the photosensitive coloring resin composition is heated and dried, the The molecular weight effect increases the viscosity of the softened coating film, thereby inhibiting the fluidization of the coating film. As another method of suppressing softening of the coating film of the photosensitive colored resin composition, a method of using another resin with a relatively high melt viscosity as a binder resin, or a method of using another functional group that promotes hydrogen bonding in the binder resin is also conceivable. A method in which a resin is used as a binder resin, but the above-mentioned copolymer containing a hydroxyalkyl (meth)acrylate unit is excellent in that the shape of the colored layer can be effectively flattened in a relatively small amount, And will not adversely affect the color tone of the coloring layer.

進而,於使用上述包含含有(甲基)丙烯酸羥烷基酯單元之共聚物之黏合劑樹脂之情形時,已將含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值調節至適當之範圍內,因此可使顯影殘渣變少。 一般而言,黏合劑樹脂之酸值越大,越容易形成黏合劑樹脂內之氫鍵,因此,若依據上述說明,則含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值越大,越可提高使著色層之形狀平坦化之效果。然而,若黏合劑樹脂之酸值過大,則會導致基板上之顯影殘渣增多。 於本發明中,藉由將含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量及源自(甲基)丙烯酸羥烷基酯之結構單元之含量調節至適當之範圍內,可有效地使著色層之形狀平坦化,因此,無需就著色層之平坦化之觀點而言使含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值變得極大,可基於使顯影殘渣變少之觀點將上述酸值設為適當之範圍。 Furthermore, in the case of using the above-mentioned binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit, the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit has been adjusted to an appropriate value Within the range, development residues can be reduced. Generally speaking, the higher the acid value of the binder resin, the easier it is to form hydrogen bonds in the binder resin. Therefore, according to the above description, the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is higher. The larger the value, the higher the effect of flattening the shape of the colored layer. However, if the acid value of the binder resin is too large, the development residue on the substrate will increase. In the present invention, by adjusting the weight average molecular weight of the copolymer containing hydroxyalkyl (meth)acrylate unit and the content of the structural unit derived from hydroxyalkyl (meth)acrylate to an appropriate range, Since the shape of the colored layer can be effectively flattened, it is not necessary to maximize the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units from the viewpoint of flattening the colored layer. From the viewpoint of reducing residues, the above acid value is set to an appropriate range.

以下,對本發明之彩色濾光片用感光性著色樹脂組合物所含有之各成分進行說明。 [色料] <染料及色澱色料> 於本發明中,使用選自由染料及色澱色料所組成之群中之至少一種作為色料。 於本發明中,染料意指可將能夠發揮著色功能之有效量溶解於溶劑中之色料。色澱色料係指利用色澱化劑使染料色澱化而成者。 染料及色澱色料係溶解於黏合劑樹脂等基質中或以極其微細之粒子狀態分散於其中,不會有損組合物之透明性,因此藉由使用選自由染料及色澱色料所組成之群中之至少一種作為色料,可使彩色濾光片之亮度變高。 Hereinafter, each component contained in the photosensitive coloring resin composition for color filters of this invention is demonstrated. [color material] <Dye and Lake Color> In the present invention, at least one selected from the group consisting of dyes and lake colorants is used as the colorant. In the present invention, the dye refers to a colorant which can be dissolved in a solvent in an effective amount capable of exerting a coloring function. The lake coloring material refers to the one formed by using a lake-forming agent to make the dye lake. The dyes and lake colorants are dissolved in the matrix such as binder resin or dispersed in the state of extremely fine particles, which will not impair the transparency of the composition. At least one of the group is used as a colorant, which can increase the brightness of the color filter.

本發明中所使用之染料及色澱色料並無特別限制。 作為染料,例如可列舉:偶氮系染料、金屬錯鹽偶氮系染料、蒽醌系染料、三芳基甲烷系染料、二苯并哌喃系染料、花青系染料、萘醌系染料、醌亞胺系染料、次甲基系染料、酞菁系染料等。 作為色澱色料,例如可列舉利用色澱化劑使如上所述之染料色澱化而成者等。色澱化劑可根據染料進行適當選擇而使用,對於陰離子染料(酸性染料),可使用產生該染料之抗衡陽離子之化合物作為色澱化劑;對於陽離子染料(鹼性染料),可使用產生該染料之抗衡陰離子之化合物作為色澱化劑。作為此種色澱化劑,可使用公知者,並無特別限定,作為用於陽離子染料(鹼性染料)之色澱化劑,例如可列舉有機陰離子之鹼金屬鹽或鹼土類金屬鹽、及無機陰離子之鹼鹽或鹼金屬鹽等;作為用於陰離子染料(酸性染料)之色澱化劑,例如可列舉產生銨陽離子之胺化合物、及具有所需金屬離子之金屬鹽等。 又,作為本發明中所使用之色澱色料,例如可較佳地使用:由一價或二價以上之陽離子染料(鹼性染料)、與二價以上之聚陰離子形成鹽所得之色澱色料、及由一價或二價以上之陰離子染料(酸性染料)、與二價以上之聚陽離子形成鹽所得之色澱色料等。 作為本發明中所使用之染料及色澱色料,具體而言,例如可列舉:日本專利特開2015-96947號公報中所記載之染料、日本專利特開2016-27149號公報中所記載之藍色染料、日本專利特開2017-16099號公報中所記載之作為色澱色料之化合物(Aa)、及染料(Ab)等。 The dyes and lake colorants used in the present invention are not particularly limited. Examples of dyes include azo-based dyes, metal zirconium salt azo-based dyes, anthraquinone-based dyes, triarylmethane-based dyes, dibenzopyran-based dyes, cyanine-based dyes, naphthoquinone-based dyes, and quinone-based dyes. Imine-based dyes, methine-based dyes, phthalocyanine-based dyes, and the like. As a lake color material, what made the above-mentioned dye lake with a lake-forming agent, etc. are mentioned, for example. The lakeing agent can be appropriately selected and used according to the dye. For anionic dyes (acid dyes), a compound that produces the counter cation of the dye can be used as a lakeing agent; for cationic dyes (basic dyes), it can be used to produce the The compound of the counter anion of the dye acts as a lake-forming agent. As such a lake-forming agent, a well-known one can be used and is not particularly limited, and examples of the lake-forming agent for cationic dyes (basic dyes) include alkali metal salts or alkaline earth metal salts of organic anions, and Alkali salts, alkali metal salts, etc. of inorganic anions; Examples of the lake-forming agent for anionic dyes (acid dyes) include amine compounds that generate ammonium cations, and metal salts having desired metal ions. In addition, as the lake coloring material used in the present invention, for example, a lake obtained by forming a salt with a cationic dye (basic dye) having a univalent or higher valence and a polyanion having a valence higher than a divalent can be preferably used. Colorants, and lake colorants obtained from monovalent or divalent anionic dyes (acid dyes) and divalent or more polycations to form salts, etc. Specific examples of the dyes and lake colorants used in the present invention include the dyes described in Japanese Patent Laid-Open No. 2015-96947 and the dyes described in Japanese Patent Laid-Open No. 2016-27149. A blue dye, a compound (Aa) as a lake color material described in Japanese Patent Laid-Open No. 2017-16099, a dye (Ab), and the like.

其中,本發明之感光性著色樹脂組合物若包含色澱色料,則即便含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值相對較大,亦容易抑制顯影殘渣之產生,就該方面而言較佳。色澱色料具有酸與鹼之鹽結構,故與羥基之親和性較高,因此色澱色料較染料及顏料而言,與含有(甲基)丙烯酸羥烷基酯單元之共聚物之相容性更良好。因此,本發明之感光性著色樹脂組合物若組合含有色澱色料與含有(甲基)丙烯酸羥烷基酯單元之共聚物,則在顯影液中之溶解性得到均勻化,藉此可抑制顯影殘渣之產生。其中,於含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值處於下述較佳之範圍內時,與色澱色料之相容性進一步提高,因此抑制顯影殘渣之效果尤其優異。Among them, if the photosensitive coloring resin composition of the present invention contains a lake coloring material, even if the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is relatively large, it is easy to suppress the generation of development residues. It is preferable in this respect. The lake colorant has a salt structure of acid and alkali, so it has a higher affinity with hydroxyl groups. Therefore, compared with dyes and pigments, the lake colorant has a better relationship with the copolymer containing hydroxyalkyl (meth)acrylate units. Capacitance is better. Therefore, when the photosensitive colored resin composition of the present invention is combined with a lake-containing colorant and a copolymer containing a hydroxyalkyl (meth)acrylate unit, the solubility in the developing solution can be made uniform, thereby suppressing the The generation of developing residues. Among them, when the hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is within the following preferable range, the compatibility with the lake color material is further improved, so the effect of suppressing the development residue is particularly excellent.

又,色澱色料中,三芳基甲烷系或二苯并哌喃系色澱色料容易提高著色層之亮度及耐熱性,就該方面而言較佳。就藍色之調色時能夠達成高亮度之觀點、以及耐熱性容易進一步提高之觀點而言,尤佳為包含三芳基甲烷系染料之色澱色料。 用於色澱色料之三芳基甲烷系染料及二苯并哌喃系染料可自公知者中進行適當選擇,並無特別限定。作為三芳基甲烷系染料,例如可列舉:C.I.鹼性藍7、8、11、26等。作為二苯并哌喃系染料,例如可列舉:C.I.酸性紅50、51、52、87、92、94、289、388、C.I.酸性紫9、30、102、硫丹明G、硫丹明B、硫丹明101、硫丹明640等二苯并哌喃系酸性染料;C.I.鹼性紫11等二苯并哌喃系鹼性染料;等。 In addition, among the lake colorants, the triarylmethane-based or dibenzopyran-based lake colorants tend to improve the brightness and heat resistance of the colored layer, and are preferred in this respect. The lake coloring material containing a triarylmethane type dye is especially preferable from a viewpoint that high brightness can be achieved at the time of blue coloring, and a viewpoint that heat resistance is easy to further improve. The triarylmethane-based dye and the dibenzopyran-based dye used for the lake colorant can be appropriately selected from known ones, and are not particularly limited. As a triarylmethane type dye, C.I. Basic Blue 7, 8, 11, 26 etc. are mentioned, for example. Examples of dibenzopyran-based dyes include C.I. Acid Red 50, 51, 52, 87, 92, 94, 289, 388, C.I. Acid Violet 9, 30, 102, Endosulfan G, Endosulfan B , Endosulfan 101, Endosulfan 640 and other dibenzopyran-based acid dyes; C.I. Basic Violet 11 and other dibenzopyran-based basic dyes; and so on.

又,本發明中所使用之色澱色料可為僅具有1個顯色性部位者,但若為具有2個以上顯色性部位者,則可獲得亮度更高且耐熱性優異之著色層,就該方面而言較佳。此處,具有2個以上顯色性部位之色澱色料係指具有1個顯色性部位之複數個染料分子與色澱化劑進行離子鍵結而成者,亦可為具有複數個顯色性部位之1個染料分子與色澱化劑進行離子鍵結而成者,亦可為具有複數個顯色性部位之複數個染料分子與色澱化劑進行離子鍵結而成者。  其中,就獲得亮度較高且耐熱性優異之著色層之觀點而言,本發明中所使用之色料較佳為包含下述通式(1)或通式(2)所表示之色澱色料,更佳為包含下述通式(1)所表示之色澱色料。下述通式(1)所表示之色澱色料係由二價以上之陽離子染料(鹼性染料)、與二價以上之聚酸陰離子形成鹽所得之色澱色料,下述通式(2)所表示之色澱色料係由一價之陽離子染料之2個以上、與二價以上之聚酸陰離子形成鹽所得之色澱色料。任一色澱色料均可能產生未與聚酸陰離子形成鹽之染料分子,尤其於下述通式(1)所表示之色澱色料中陽離子之數量與陰離子之數量不同之情形時,容易產生未與聚酸陰離子形成鹽之染料分子。未與聚酸陰離子形成鹽之染料分子可能與含有(甲基)丙烯酸羥烷基酯單元之共聚物中之酸性基形成鹽。下述通式(1)或通式(2)所表示之色澱色料不僅酸與鹼之鹽結構與上述共聚物中之(甲基)丙烯酸羥烷基酯單元之親和性較高,而且未與聚酸陰離子形成鹽之染料分子還可能與上述共聚物中之具有酸性基之結構單元形成鹽,因此包含下述通式(1)或通式(2)所表示之色澱色料之本發明之感光性著色樹脂組合物會形成由該色澱色料與上述共聚物締合而成之複合物,阻礙熱運動之效果變大,因此推定耐熱性提高。  又,下述通式(1)或通式(2)所表示之色澱色料亦藉由具有酸與鹼之鹽結構,而與含有(甲基)丙烯酸羥烷基酯單元之共聚物之相容性良好,因此即便含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值相對較大,亦可抑制顯影殘渣之產生。  其中,於含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值處於下述較佳之範圍內之情形時,與下述通式(1)或通式(2)所表示之色澱色料之相容性進一步提高,因此抑制顯影殘渣之效果尤其優異。於含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值及羥值處於下述較佳之範圍內之情形時,容易形成與下述通式(1)或通式(2)所表示之色澱色料締合而成之複合物,因此提高耐熱性之效果尤其優異。In addition, the lake coloring material used in the present invention may have only one color developing site, but if it has two or more color developing sites, a colored layer with higher brightness and excellent heat resistance can be obtained , which is better in this regard. Here, the lake coloring material with two or more color rendering sites refers to the one formed by ionic bonding between a plurality of dye molecules having one color rendering site and a lake forming agent, and may also be a plurality of color rendering sites. One dye molecule in a chromogenic site is ionically bonded to the lake agent, or a plurality of dye molecules having a plurality of color rendering sites are ionically bonded with the lake agent. Among them, from the viewpoint of obtaining a colored layer with high brightness and excellent heat resistance, the colorant used in the present invention preferably contains a lake represented by the following general formula (1) or general formula (2). It is more preferable to contain a lake coloring material represented by the following general formula (1). The lake coloring material represented by the following general formula (1) is a lake coloring material obtained by forming a salt with a cationic dye (basic dye) with a divalent or more and a polyacid anion with a divalent or more, the following general formula ( 2) The lake coloring material represented is a lake coloring material obtained by forming a salt with two or more monovalent cationic dyes and a divalent or more polyacid anion. Any lake colorant may produce dye molecules that do not form salts with polyacid anions, especially when the number of cations in the lake colorant represented by the following general formula (1) is different from the number of anions, it is easy to generate Dye molecules that do not form salts with polyacid anions. Dye molecules that do not form salts with polyacid anions may form salts with acidic groups in copolymers containing hydroxyalkyl (meth)acrylate units. The lake coloring material represented by the following general formula (1) or general formula (2) not only has a higher affinity between the salt structure of acid and alkali and the hydroxyalkyl (meth)acrylate unit in the above-mentioned copolymer, but also The dye molecules that do not form salts with polyacid anions may also form salts with the structural units with acidic groups in the above-mentioned copolymers, so they include those of the lake colorants represented by the following general formula (1) or general formula (2). The photosensitive colored resin composition of the present invention forms a complex formed by associating the lake coloring material and the above-mentioned copolymer, and the effect of inhibiting thermal motion becomes large, so it is presumed that the heat resistance is improved. In addition, the lake coloring material represented by the following general formula (1) or general formula (2) also has a salt structure with an acid and a base, and the copolymer containing a hydroxyalkyl (meth)acrylate unit is also formed. The compatibility is good, so even if the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is relatively large, the generation of development residues can be suppressed. Among them, when the hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units is in the following preferable range, it is different from the lake represented by the following general formula (1) or general formula (2). The compatibility of the colorant is further improved, so the effect of suppressing the development residue is particularly excellent. When the acid value and hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units are in the following preferable ranges, it is easy to form the same compound represented by the following general formula (1) or general formula (2). The complex formed by the association of the lake color materials, so the effect of improving heat resistance is particularly excellent.

(通式(1)所表示之色澱色料) 以下,對本發明中被較佳地使用之通式(1)所表示之色澱色料進行詳細說明。 (Lake color material represented by general formula (1)) Hereinafter, the lake coloring material represented by the general formula (1) preferably used in the present invention will be described in detail.

[化2] 通式(1)

Figure 02_image007
(通式(1)中,A為與N直接鍵結之碳原子不具有π鍵之a價有機基,該有機基表示至少在與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,於碳鏈中可包含雜原子;B c-表示c價聚酸陰離子;R i~R v分別獨立地表示氫原子、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分別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可分別相同,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;e為0或1,於e為0時不存在鍵;f及g表示0以上4以下之整數,f+e及g+e為0以上4以下;存在複數個之e、f及g可分別相同,亦可不同) [Chemical 2] General formula (1)
Figure 02_image007
(In the general formula (1), A is an a-valent organic group that does not have a π bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain; B c- represents a c-valent polyacid anion; R i to R v independently represent a hydrogen atom, an alkyl group that may have a substituent Or an aryl group that may have a substituent, R ii and R iii , R iv and R v can be bonded to form a ring structure; R vi and R vii independently represent an alkyl group that may have a substituent group, and a group that may have a substituent group. An alkoxy group, a halogen atom or a cyano group; Ar 1 represents a divalent aromatic group which may have a substituent; R i to R vii and Ar 1 present in plural may be the same or different respectively; a and c represent 2 or more b and d represent integers greater than or equal to 1; e is 0 or 1, and no bond exists when e is 0; f and g represent integers greater than 0 and less than 4, and f+e and g+e are greater than or equal to 0 and less than 4; e, f and g may be the same or different respectively)

上述通式(1)所表示之色料由於包含二價以上之陰離子、與二價以上之陽離子,因此於該色料之凝聚體中,可形成複數個分子經由離子鍵而締合之分子締合物,而非陰離子與陽離子僅以1分子對1分子之形式離子鍵結在一起,因此表觀之分子量較先前之色澱色料之分子量大幅增大。藉由形成此種分子締合物,使得固體狀態下之凝聚力進一步變高,降低熱運動,可抑制離子對之解離或陽離子部之分解,從而推定較先前之色澱色料更不易褪色。Since the colorant represented by the above-mentioned general formula (1) contains an anion of divalent or more and a cation of divalent or more, in the aggregate of the colorant, a molecular association in which a plurality of molecules are associated through ionic bonds can be formed. The non-anion and the cation are only ionically bonded together in the form of 1 molecule to 1 molecule, so the apparent molecular weight is greatly increased compared with the previous lake pigment. By forming such molecular associations, the cohesion force in the solid state is further increased, the thermal motion is reduced, and the dissociation of ion pairs or the decomposition of cation moieties can be suppressed, so that it is presumed that the color of the lake is less likely to fade than the previous color lake.

上述通式(1)中之A為與N(氮原子)直接鍵結之碳原子不具有π鍵之a價有機基,該有機基表示至少在與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,於碳鏈中可包含O(氧原子)、S(硫原子)、N(氮原子)等雜原子。即,該有機基表示至少在與N直接鍵結之末端具有飽和脂肪族烴基且於碳鏈中可包含O、S、N等雜原子之脂肪族烴基、或者具有在與N直接鍵結之末端具有飽和脂肪族烴基之脂肪族烴基且於碳鏈中可包含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,因此陽離子性之顯色部位所具有之色調或透過率等色特性可不受連結基A或其他顯色部位之影響,而保持與單體相同之顏色。A in the above-mentioned general formula (1) is an a-valent organic group whose carbon atom directly bonded to N (nitrogen atom) does not have a π bond, and the organic group represents a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N The aliphatic hydrocarbon group, or the aromatic group having the aliphatic hydrocarbon group, may contain heteroatoms such as O (oxygen atom), S (sulfur atom), N (nitrogen atom), etc. in the carbon chain. That is, the organic group means an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N and may contain heteroatoms such as O, S, N, etc. in the carbon chain, or an aliphatic hydrocarbon group having a terminal directly bonded to N An aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group and which may contain heteroatoms such as O, S, N, etc. in the carbon chain. Since the carbon atom directly bonded to N does not have a π bond, the color properties such as hue or transmittance of the cationic color-developing site can remain the same as the monomer without being affected by the linking group A or other color-developing sites. color.

於A中,關於至少在與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,便可為直鏈、支鏈或環狀之任一者,末端以外之碳原子可具有不飽和鍵,亦可具有取代基,於碳鏈中可包含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,關於具有上述脂肪族烴基之芳香族基,可列舉具有至少在與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,就骨架之牢固性之觀點而言,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,可列舉包含環己烷、環戊烷、降𦯉烷、雙環[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,例如可列舉包含苯環、萘環之基等。例如於A為二價有機基之情形時,可列舉碳數1~20之直鏈、支鏈、或環狀之伸烷基、或者苯二甲基等將碳數1~20之伸烷基取代2個後所得之芳香族基等。 In A, the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be straight chain, branched chain or cyclic as long as the carbon atom at the terminal directly bonded to N does not have a π bond In any of the shapes, the carbon atoms other than the terminal may have an unsaturated bond or a substituent, and may contain O, S, and N in the carbon chain. For example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc. may be included, and a hydrogen atom may be further substituted with a halogen atom or the like. In A, the aromatic group having the above-mentioned aliphatic hydrocarbon group includes a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, and may have The substituent may be a heterocyclic ring containing O, S and N. Among them, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group from the viewpoint of the firmness of the skeleton. Examples of the cyclic aliphatic hydrocarbon group include cyclohexane, cyclopentane, noralkane, bicyclo[2.2.2]octane, tricyclo[ 5.2.1.02,6 ]decane, and adamantane groups. . 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, a linear, branched, or cyclic alkylene having 1 to 20 carbon atoms, or an alkylene having 1 to 20 carbon atoms, such as a xylylene group, can be mentioned. The aromatic group obtained by substituting two of them, etc.

於本發明中,就兼顧牢固性、與分子移動之自由度,提高耐熱性之觀點而言,A較佳為具有2個以上環狀脂肪族烴基,在與N直接鍵結之末端具有飽和脂肪族烴基,且於碳鏈中可包含O、S、N之脂肪族烴基。A更佳為具有2個以上之伸環烷基,在與N直接鍵結之末端具有飽和脂肪族烴基,且於碳鏈中可包含O、S、N之脂肪族烴基,其中,進而較佳為具有2個以上環狀脂肪族烴基經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可分別相同,亦可不同,例如可列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, A preferably has two or more cyclic aliphatic hydrocarbon groups, and has a saturated aliphatic at the terminal directly bonded to N, from the viewpoint of achieving both firmness and freedom of molecular movement and improving heat resistance. It is an aliphatic hydrocarbon group, and may contain O, S, N aliphatic hydrocarbon groups in the carbon chain. A is more preferably a cycloextended alkyl group having two or more, a saturated aliphatic hydrocarbon group at the terminal directly bonded to N, and an aliphatic hydrocarbon group that may contain O, S, and N in the carbon chain, among which, more preferable It is a structure in which two or more cyclic aliphatic hydrocarbon groups are linked by linear or branched aliphatic hydrocarbon groups. Two or more cyclic aliphatic hydrocarbon groups may be the same or different, and examples thereof include the same ones as the above-mentioned cyclic aliphatic hydrocarbon groups, among which cyclohexane and cyclopentane are preferred.

於本發明中,就耐熱性之觀點而言,其中,上述A較佳為下述通式(1a)所表示之取代基。In the present invention, from the viewpoint of heat resistance, the above-mentioned A is preferably a substituent represented by the following general formula (1a).

[化3] 通式(1a)

Figure 02_image009
(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分別獨立地表示碳數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分別獨立地表示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可彼此相通,亦可不同) [Chemical 3] General formula (1a)
Figure 02_image009
(In general formula (1a), R xi represents an alkylene group having 1 to 3 or less carbon atoms which may have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms or less as a substituent, and R xii and R xiii each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, p represents an integer of 1 to 3 or less, and q and r each independently represent 0 to 4 or less Integer of ; when there are plural R xi , R xii , R xiii and r, the plural R xi , R xii , R xiii and r may be the same or different)

就牢固性與顯色部位之熱運動之兼顧性優異,耐熱性提高之觀點而言,作為R xi中之碳數1以上3以下之伸烷基,可列舉亞甲基、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,可列舉甲基、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,可列舉甲氧基、乙氧基、丙氧基、丁氧基,可為直鏈狀,亦可具有支鏈。 From the viewpoint of being excellent in both firmness and thermal motion of the color-developing site and improving heat resistance, examples of the alkylene group having 1 to 3 carbon atoms in R xi include methylene group, ethylidene group, and ethylene group. propyl group, etc., among them, methylene group or ethylidene group is preferable, and methylene group is more preferable. Examples of the alkyl group having from 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Moreover, as a C1-4 or less alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group can be mentioned, and a straight chain may be sufficient as it, and a branched chain may be sufficient.

關於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,可列舉與上述R xi可具有之取代基相同者。 Among R xii and R xiii , the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms or less can be exemplified by the same substituents as those that R xi may have.

於通式(1a)中,就耐熱性之觀點而言,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,但就耐熱性之觀點而言,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), from the viewpoint of heat resistance, it is preferable that the number of cyclohexane (cyclohexylene) is 2 or more and 4 or less, that is, p is 1 or more and 3 or less, and it is more preferable that p is 1 or more and 2 or less. In addition, the number of substituents R xii and R xiii of the cyclohexylene group is not particularly limited, but from the viewpoint of heat resistance, it is preferably 1 or more and 3 or less, more preferably 1 or more and 2 the following. That is, it is preferable that q and r are an integer of 1 or more and 3 or less, and it is preferable that q and r are an integer of 1 or more and 2 or less.

作為此種連結基A之較佳之具體例,可列舉以下者,但並不限於其等。As a preferable specific example of such a linking group A, the following are mentioned, but it is not limited to these.

[化4]

Figure 02_image011
[hua 4]
Figure 02_image011

R i~R v中之烷基並無特別限定。例如可列舉碳數1~20之直鏈、支鏈狀或環狀之烷基等,其中,可列舉碳數為1~8之直鏈或支鏈之烷基,就亮度及耐熱性之觀點而言,可列舉碳數為1~5之直鏈或支鏈之烷基,R i~R v中之烷基可列舉乙基或甲基。作為烷基可具有之取代基,並無特別限定,例如可列舉芳基、鹵素原子、羥基、烷氧基等,作為經取代之烷基,可列舉如苄基之芳烷基等。 R i~R v中之芳基並無特別限定。例如可列舉苯基、萘基等。作為芳基可具有之取代基,例如可列舉烷基、鹵素原子、烷氧基、羥基等。 其中,就化學穩定性之觀點而言,作為R i~R v,分別獨立地較佳為氫原子、碳數1~5之烷基、苯基,或者R ii與R iii、R iv與R v鍵結而形成了吡咯啶環、哌啶環、𠰌啉環。 The alkyl group in R i to R v is not particularly limited. For example, straight-chain, branched or cyclic alkyl groups having 1 to 20 carbon atoms can be cited, among which, straight-chain or branched alkyl groups having 1 to 8 carbon atoms can be cited. From the viewpoint of brightness and heat resistance For example, a linear or branched alkyl group having 1 to 5 carbon atoms can be mentioned, and an ethyl group or a methyl group can be mentioned as the alkyl group in R i to R v . The substituent which the alkyl group may have is not particularly limited, and examples thereof include aryl groups, halogen atoms, hydroxyl groups, alkoxy groups, and the like, and examples of the substituted alkyl groups include aralkyl groups such as benzyl groups. 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 alkoxy group, a hydroxyl group, etc. are mentioned, for example. Among them, from the viewpoint of chemical stability, R i to R v are each independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ii and R iii , and R iv and R . v -bonded to form a pyrrolidine ring, a piperidine ring, and a pyridine ring.

就耐熱性之觀點而言,較佳為R ii~R v中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。R ii~R v中之至少一者具有環烷基、或芳基,這使得由位阻引起之分子間交互作用減少,因此可抑制顯色部位受熱之影響,由此認為耐熱性優異。 From the viewpoint of heat resistance, at least one of R ii to R v is preferably an optionally substituted cycloalkyl group or an optionally substituted aryl group. At least one of R ii to R v has a cycloalkyl group or an aryl group, which reduces the intermolecular interaction due to steric hindrance, thereby suppressing the influence of heat on the color-developing site, and is considered to be excellent in heat resistance.

就耐熱性之觀點而言,較佳為R ii~R v中至少一者為下述通式(1b)或下述通式(1c)所表示之取代基。 From the viewpoint 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5] 通式(1b)

Figure 02_image013
(通式(1b)中,R xiv、R xv、及R xvi分別獨立地表示氫原子、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) [Chem. 5] General formula (1b)
Figure 02_image013
(In the general formula (1b), R xiv , R xv , and R xvi each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted alkyl group having 1 to 4 carbon atoms the following alkoxy)

[化6] 通式(1c)

Figure 02_image015
(通式(1c)中,R xvii、R xviii、及R xix分別獨立地表示氫原子、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) [Chem. 6] General formula (1c)
Figure 02_image015
(In general formula (1c), R xvii , R xviii , and R xix each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, or an optionally substituted group having 1 to 4 carbon atoms 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,可列舉甲基、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,可列舉甲氧基、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,可列舉鹵素原子、羥基等。 Examples of the alkyl group 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, and may be linear. , can also have branched chains. Moreover, as a C1-4 or less alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group can be mentioned, and a straight chain may be sufficient as it, and a branched chain may be sufficient. As a substituent which the said alkyl group and an 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,就耐熱性之觀點而言,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-mentioned general formula (1b), from the viewpoint of heat resistance, it is preferable that at least one of R xiv , R xv , and R xvi be carbon number 1 which may have a substituent An alkyl group of 4 or less, or an alkoxy group of 1 to 4 or less carbon atoms which may have a substituent, more preferably at least one of R xiv and R xv is an alkane of 1 to 4 carbon atoms which may have a substituent group, or an alkoxy group having 1 or more carbon atoms and 4 or less 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,就耐熱性之觀點而言,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。 Moreover, in the case of having a substituent represented by the above-mentioned general formula (1c), from the viewpoint of heat resistance, it is preferable that at least one of R xvii , R xviii , and R xix be a carbon which may have a substituent An alkyl group having 1 or more and 4 or less carbon atoms, or an optionally substituted alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms, more preferably, at least one of R xvii and R xviii is an optionally substituted carbon group having 1 to 4 carbon atoms. an alkyl group, or an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms which may have a substituent.

作為通式(1b)所表示之取代基、及通式(1c)所表示之取代基之較佳之具體例,可列舉以下者,但並不限於其等。Preferred specific examples of the substituent represented by the general formula (1b) and the substituent represented by the general formula (1c) include the following, but are not limited thereto.

[化7]

Figure 02_image017
[hua 7]
Figure 02_image017

R vi及R vii分別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,可列舉甲基、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,例如可列舉芳基、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,可列舉甲氧基、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,例如可列舉芳基、鹵素原子、羥基、烷氧基等。 作為R vi及R vii中之鹵素原子,例如可列舉: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可分別相同,亦可不同。 又,R vi及R vii可於三芳基甲烷骨架、或二苯并哌喃骨架內之具有共振結構之芳香環之任一部位進行取代,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至間位。 R vi and R vii each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, a halogen atom or a cyano group. The alkyl group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, more preferably an alkane having 1 to 4 carbon atoms or less. base. Examples of the alkyl group having from 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group, which may be linear or branched. Although 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. Further, the alkoxy group in R vi and R vii is not particularly limited, but is preferably a straight-chain or branched alkoxy group having 1 to 8 carbon atoms, more preferably 1 or more carbon atoms 4 or less alkoxy groups. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and may be linear or branched. Although 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 R vi and R vii , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The substitution numbers of R vi and R vii , that is, f and g each independently represent an integer of 0 or more and 4 or less, and among them, preferably 0 or more and 2 or less, more preferably 0 or more and 1 or less. A plurality of f and g may be the same or different, respectively. In addition, R vi and R vii can be substituted at any position of the aromatic ring having a resonance structure in the triarylmethane skeleton or the dibenzopyran skeleton, wherein, preferably -NR ii R iii or -NR The substitution position of the amine group represented by iv R v is taken as a reference, and it is substituted to the meta position.

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,除苯環以外,亦可列舉: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、二苯甲烷、三苯甲烷、茋等鏈狀多環式烴。關於該鏈狀多環式烴,可如二苯醚等般在鏈狀骨架中具有O、S、N。另一方面,作為雜環基中之雜環,可列舉: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、以及可經其等取代之苯基等作為取代基。 The divalent aromatic group in Ar 1 is not particularly limited. In addition to the aromatic hydrocarbon group containing a carbocyclic ring, the aromatic group in Ar 1 may be a heterocyclic group. As the aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to the benzene ring, condensed polycyclic aromatic hydrocarbons such as a naphthalene ring, a tetralin ring, an indene ring, a perylene ring, an anthracene ring, and a phenanthrene ring; Chain polycyclic hydrocarbons such as benzene, diphenylmethane, triphenylmethane, and stilbene. The chain polycyclic hydrocarbon may have O, S, and N in the chain skeleton like diphenyl ether or the like. On the other hand, as the heterocyclic ring in the heterocyclic group, there may be mentioned 5-membered heterocyclic rings such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; piperane, pyrone, pyridine, pyrone, 6-membered heterocycles such as pyrimidine, pyrimidine, pyridine, etc.; benzofuran, benzothiophene, indole, carbazole, coumarin, benzopyrone, quinoline, isoquinoline, acridine, quinoline, Condensed polycyclic heterocycles such as quinazoline and quinoline. These aromatic groups may further have an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a phenyl group which may be substituted therewith, or the like 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,可調整為所需顏色。 A plurality of R i to R vii and Ar 1 present in one molecule may be the same or different. The desired color can be adjusted by the combination of R i to R vii and Ar 1 .

A中之價數a係構成陽離子之顯色性陽離子部位之數,a為2以上之整數。於該色澱色料中,陽離子之價數a為2以上,因此耐熱性優異。a之上限並無特別限定,但就製造之容易性之觀點而言,a較佳為4以下,更佳為3以下。The valence a in A is the number of chromogenic cationic sites constituting the cation, and a is an integer of 2 or more. In this lake color material, since the valence a of the cation is 2 or more, it is excellent in heat resistance. The upper limit of a is not particularly limited, but from the viewpoint of ease of manufacture, a is preferably 4 or less, more preferably 3 or less.

於通式(1)所表示之色料中,就耐熱性優異,容易抑制加熱時之變色之觀點而言,陽離子部較佳為分子量為1200以上,較佳為1300以上。In the colorant represented by the general formula (1), the molecular weight of the cation part is preferably 1200 or more, more preferably 1300 or more, from the viewpoint of being excellent in heat resistance and easily suppressing discoloration during heating.

於通式(1)所表示之色料中,就亮度較高且耐熱性優異之觀點而言,陰離子部(B c-)為c價聚酸陰離子,且為二價以上之陰離子。 In the colorant represented by the general formula (1), from the viewpoint of high brightness and excellent heat resistance, the anion part (B c- ) is a c-valent polyacid anion, and is an anion of divalent or higher.

作為由複數個含氧酸縮合而成之聚酸陰離子,可為異聚酸陰離子(M mO n) c-,亦可為雜聚酸陰離子(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,l表示雜原子之組成比。作為多原子M,例如可列舉Mo、W、V、Ti、Nb等。又,作為雜原子X,例如可列舉Si、P、As、S、Fe、Co等。又,一部分亦可含有Na 或H 等抗衡陽離子。 其中,就耐熱性優異之觀點而言,較佳為具有選自鎢(W)及鉬(Mo)中之一種以上之元素之聚酸。 作為此種聚酸,例如可列舉:作為異聚酸之鎢酸根離子[W 10O 32] 4-、鉬酸根離子[Mo 6O 19] 2-;或者作為雜聚酸之磷鎢酸根離子[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。作為包含鎢(W)及鉬(Mo)之至少一種之聚酸,就耐熱性之觀點、及原料獲取之容易性之觀點而言,上述中,較佳為雜聚酸,進而更佳為包含磷(P)之雜聚酸。 進而,就耐熱性方面而言,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-之任一者。 As the polyacid anion condensed from a plurality of oxoacids , it may be a heteropolyacid anion (M m On ) c- or a heteropolyacid anion (X l M m O n ) c- . In the above ionic formula, M represents polyatoms, X represents heteroatoms, m represents the compositional ratio of polyatoms, n represents the compositional ratio of oxygen atoms, and l represents the compositional ratio of heteroatoms. As polyatomic M, Mo, W, V, Ti, Nb etc. are mentioned, for example. Moreover, as a hetero atom X, Si, P, As, S, Fe, Co, etc. are mentioned, for example. Moreover, a part may contain counter cations, such as Na + and H + . Among them, from the viewpoint of being excellent in heat resistance, a polyacid having one or more elements selected from tungsten (W) and molybdenum (Mo) is preferred. Examples of such polyacids include tungstate ions [W 10 O 32 ] 4- and molybdate ions [Mo 6 O 19 ] 2- as heteromeric acids; or phosphotungstate ions as heteropoly acids [ PW 12 O 40 ] 3- , [P 2 W 18 O 62 ] 6- , silicotungstic acid ion [SiW 12 O 40 ] 4- , phosphomolybdate ion [PMo 12 O 40 ] 3- , silico-molybdate ion [ SiMo 12 O 40 ] 4- , phosphotungstomolybdate ion [PW 12 -s Mo s O 40 ] 3- (s is an integer of 1 to 11) , [P 2 W 18 -t Mo t O 62 ] 6- (t is an integer of 1 or more and 17 or less), silicotungstic molybdate ion [SiW 12 - u Mo u O 40 ] 4- (u is an integer of 1 or more and 11 or less), and the like. As the polyacid containing at least one of tungsten (W) and molybdenum (Mo), from the viewpoint of heat resistance and the ease of obtaining raw materials, among the above, a heteropolymeric acid is preferred, and more preferred is a polyacid containing Heteromeric acid of phosphorus (P). Furthermore, in terms of heat resistance, phosphotungstic molybdate ions [PW 10 Mo 2 O 40 ] 3- , [PW 11 Mo 1 O 40 ] 3- , and phosphotungstic acid ions [PW 12 O 40 ] are further preferred. 3- any one.

通式(1)中之b表示陽離子之數,d表示分子締合物中之陰離子之數,b及d表示1以上之整數。於b為2以上之情形時,於分子締合物中存在複數個之陽離子可為單獨一種,亦可為兩種以上之組合。又,於d為2以上之情形時,於分子締合物中存在複數個之陰離子可為單獨一種,亦可為兩種以上之組合。 就藉由與含有(甲基)丙烯酸羥烷基酯單元之共聚物之組合而容易提高耐熱性之觀點而言,通式(1)中之b與d較佳為彼此不同之整數。於通式(1)中之b與d為彼此不同之整數之情形時,作為陽離子之染料分子容易與含有(甲基)丙烯酸羥烷基酯單元之共聚物進行交互作用,而容易形成由色料與該共聚物締合而成之複合物,因此阻礙熱運動之效果變大,從而推定耐熱性提高。 In the general formula (1), b represents the number of cations, d represents the number of anions in the molecular association, and b and d represent an integer of 1 or more. When b is 2 or more, a plurality of cations present in the molecular association may be one type alone or a combination of two or more types. Moreover, when d is 2 or more, the anion which exists in a plurality of molecular associations may be a single type or a combination of two or more types. From the viewpoint of easily improving heat resistance by combining with a copolymer containing a hydroxyalkyl (meth)acrylate unit, b and d in the general formula (1) are preferably integers different from each other. In the case where b and d in the general formula (1) are integers different from each other, the dye molecules as cations are likely to interact with the copolymer containing hydroxyalkyl (meth)acrylate units, and it is easy to form a different color. Since the compound formed by the association of the material and the copolymer, the effect of inhibiting thermal motion is increased, and it is presumed that the heat resistance is improved.

通式(1)中之e為整數0或1,於e為0時不存在鍵。e=0表示三芳基甲烷骨架,e=1表示二苯并哌喃骨架。存在複數個之e可相同亦可不同。關於本發明中所使用之通式(1)所表示之色澱色料,可較佳地使用至少包含三芳基甲烷骨架者。 再者,作為通式(1)所表示之色澱色料,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。 通式(1)所表示之色澱色料可單獨使用一種,亦可組合兩種以上而使用。 e in the general formula (1) is an integer of 0 or 1, and when e is 0, no bond exists. e=0 represents a triarylmethane skeleton, and e=1 represents a dibenzopyran skeleton. A plurality of e may be the same or different. Regarding the lake coloring material represented by the general formula (1) used in the present invention, one containing at least a triarylmethane skeleton can be preferably used. In addition, as a lake color material represented by general formula (1), for example, it can refer to the specification of International Publication No. 2012/144520, and the specification of International Publication No. 2018/003706 can be prepared. The lake coloring material represented by the general formula (1) may be used alone or in combination of two or more.

(通式(2)所表示之色澱色料) 其次,對本發明中被較佳地使用之通式(2)所表示之色澱色料進行詳細說明。 (Lake color material represented by general formula (2)) Next, the lake coloring material represented by the general formula (2) preferably used in the present invention will be described in detail.

[化8] 通式(2)

Figure 02_image019
(通式(2)中,R I~R VI分別獨立地表示氫原子、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分別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可分別相同,亦可不同;E m-表示m價聚酸陰離子;  m表示2以上之整數;j為0或1,於j為0時不存在鍵;k及l表示0以上4以下之整數,k+j及l+j為0以上4以下;存在複數個之j、k及l可分別相同,亦可不同) [Chemical 8] General formula (2)
Figure 02_image019
(In the general formula (2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R I and R II , R III and R IV , R V It can 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 The divalent aromatic heterocyclic group, there are plural R I to R VIII and Ar 2 which may be the same or different; E m- represents an m-valent polyacid anion; m represents an integer of 2 or more; j is 0 or 1. When j is 0, there is no bond; k and l represent integers above 0 and below 4, and k+j and l+j are above 0 and below 4; there are multiple j, k and l which may be the same or different respectively)

通式(2)中,R I~R VI分別獨立地表示氫原子、可具有取代基之烷基或可具有取代基之芳基,且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分別可與上述通式(1)之R i~R v相同。 通式(2)中,R VII及R VIII分別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,其等亦可與上述通式(1)之R vi及R vii相同。 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可與上述通式(1)之Ar 1中之芳香族雜環基相同。 又,通式(2)中,E m-表示m價聚酸陰離子,該m價聚酸陰離子可與上述通式(1)之c價聚酸陰離子相同。 In the general formula (2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and R I and R II , R III and R IV , and R V It can bond with R VI 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 which may have a substituent, an alkoxy group which may have a substituent, a halogen atom or a cyano group. R vi and R vii are the same. In the general formula (2), Ar 2 represents a divalent aromatic heterocyclic group which may have a substituent, and this Ar 2 may be the same as the aromatic heterocyclic group in Ar 1 of the above-mentioned general formula (1). In addition, 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).

通式(2)中,m表示陽離子之數及陰離子之數,且表示2以上之整數。通式(2)中存在複數個之陽離子可為單獨一種,亦可為兩種以上之組合。又,陰離子同樣可為單獨一種,亦可為兩種以上之組合。 通式(2)中,j為0或1,於j為0時不存在鍵。通式(2)中之j可與上述通式(1)之e相同。又,通式(2)中之k及l可與上述通式(1)之f及g相同。 再者,作為通式(2)所表示之色澱色料,例如可參考日本專利特開2017-16099號公報進行製備。 通式(2)所表示之色澱色料可單獨使用一種,亦可組合兩種以上而使用。 In the general formula (2), m represents the number of cations and the number of anions, and represents an integer of 2 or more. In the general formula (2), a plurality of cations may be used alone or in combination of two or more. In addition, the anion may also be a single type or a combination of two or more types. In the general formula (2), j is 0 or 1, and when j is 0, no bond exists. j in the general formula (2) may be the same as e in the above-mentioned general formula (1). In addition, k and l in the general formula (2) may be the same as f and g in the above-mentioned general formula (1). In addition, as a lake color material represented by general formula (2), it can refer to Japanese Patent Laid-Open No. 2017-16099, for example, and can be prepared. The lake coloring material represented by the general formula (2) may be used alone or in combination of two or more.

關於本發明中所使用之色料,亦可為了調整色相而包含複數種色料。 於本發明中所使用之色料包含上述通式(1)或通式(2)所表示之色澱色料,且為了調整色相而進而包含其他色料之情形時,作為該其他色料,就可獲得高亮度之著色層之觀點而言,較佳為選自由二苯并哌喃系染料、與上述通式(1)或通式(2)所表示之色澱色料不同之二苯并哌喃系染料之色澱色料、及C.I.顏料藍15:6所組成之群中之至少一種。 Regarding the colorant used in the present invention, a plurality of colorants may be included in order to adjust the hue. When the colorant used in the present invention includes the lake colorant represented by the general formula (1) or the general formula (2), and further includes other colorants in order to adjust the hue, as the other colorant, From the viewpoint of obtaining a high-brightness coloring layer, it is preferably selected from dibenzopyran-based dyes and diphenyl dyes different from the lake coloring materials represented by the general formula (1) or (2) above. At least one of the group consisting of the lake colorant of the pyran-based dye and C.I. Pigment Blue 15:6.

(二苯并哌喃系染料) 作為與上述通式(1)或通式(2)所表示之色澱色料組合而使用之二苯并哌喃系染料,只要為分子內具有二苯并哌喃骨架之染料即可,可使用公知之二苯并哌喃系染料,並無特別限定。其中,就可獲得高亮度之著色層之觀點而言,較佳為下述通式(3)或通式(4)所表示之二苯并哌喃系染料。 (Dibenzopyran-based dyes) The dibenzopyran-based dye used in combination with the lake colorant represented by the general formula (1) or the general formula (2) may be a dye having a dibenzopyran skeleton in the molecule. A well-known dibenzopyran-based dye is used, and is not particularly limited. Among them, a dibenzopyran-based dye represented by the following general formula (3) or general formula (4) is preferred from the viewpoint of obtaining a high-brightness colored layer.

於本發明之感光性著色樹脂組合物中,藉由使用下述通式(3)所表示之二苯并哌喃系染料,可提高著色層之亮度及耐光性。In the photosensitive colored resin composition of the present invention, by using the dibenzopyran-based dye represented by the following general formula (3), the brightness and light resistance of the colored layer can be improved.

[化9] 通式(3)

Figure 02_image021
(通式(3)中,R 1及R 2分別獨立地為烷基或芳基,R 3及R 4分別獨立地為芳基或雜芳基) [Chemical 9] General formula (3)
Figure 02_image021
(In the general formula (3), R 1 and R 2 are each independently an alkyl group or an aryl group, and R 3 and R 4 are each independently an aryl group or a heteroaryl group)

上述通式(3)所表示之二苯并哌喃系染料之特徵在於:除具有二苯并哌喃作為基本骨架以外,還僅具有1個包含SO 2之官能基,與氮原子鍵結之R 1~R 4之任一者均非氫原子,R 3及R 4為芳基或雜芳基,因此氮原子上不會僅鍵結有飽和烴基,不具有鹼金屬離子。藉由使用具有此種特徵之上述通式(3)所表示之二苯并哌喃系染料,而使著色層之亮度及耐光性提高,關於上述作用,雖有不明之處,但考慮如下。上述通式(3)所表示之二苯并哌喃系染料具有陽離子性之二苯并哌喃骨架、及1個陰離子性之-SO 3 -基,因此在電性上穩定。因此,推定即便使其分散於溶劑中,亦不解離而穩定性優異。又,氮原子具有芳基或雜芳基之類之芳香族性取代基,因此該氮原子所具有之孤電子對不僅與二苯并哌喃骨架,還與該芳基或雜芳基進行共振,由此推定分子更穩定。進而,氮原子未直接與氫原子鍵結,因此氫原子不會自氮原子脫離而導致該色料不穩定。基於上述內容,上述通式(3)所表示之二苯并哌喃系染料即便於光照射下亦穩定,耐光性優異,藉由使用該色料,可形成耐光性優異之著色層。又,色料之褪色得到抑制,結果可提高著色層之亮度。 又,關於上述通式(3)所表示之二苯并哌喃系染料,可將R 3及R 4設為彼此不同者,因此分子設計之範圍廣泛,藉此分光特性等之調整範圍亦廣泛,因此容易使該色料接近目標色度,進而容易提高亮度。 又,上述通式(3)所表示之二苯并哌喃系染料具有陽離子性之二苯并哌喃骨架、及僅1個陰離子性之-SO 3 -基,僅具有內鹽,因此不具有鹼金屬離子。藉此,於使用上述通式(3)所表示之二苯并哌喃系染料來形成著色層之情形時,在製成液晶面板時可抑制鹼金屬離子自著色層溶出至液晶層,因此可獲得電氣可靠性優異之著色層。 進而,上述通式(3)所表示之二苯并哌喃系染料之包含SO 2之官能基僅有1個,因此與PGMEA(Propylene Glycol Monomethyl Ether Acetate,丙二醇單甲醚乙酸酯)等低極性溶劑之親和性變高。又,於使上述通式(3)所表示之二苯并哌喃系染料溶解於溶劑中之情形時,可使用極性相對較低之溶劑,因此可提高感光性著色樹脂組合物之穩定性。 The characteristics of the dibenzopyran-based dye represented by the above general formula (3) are: in addition to having dibenzopyran as the basic skeleton, it also has only one functional group containing SO 2 , which is bonded to a nitrogen atom. Any one of R 1 to R 4 is not a hydrogen atom, and R 3 and R 4 are aryl groups or heteroaryl groups, so nitrogen atoms are not bound to only saturated hydrocarbon groups and do not have alkali metal ions. By using the dibenzopyran-based dye represented by the above-mentioned general formula (3) having such characteristics, the brightness and light resistance of the colored layer can be improved. Although there are unknown points about the above effects, the following is considered. The dibenzopyran-based dye represented by the general formula (3) has a cationic dibenzopyran skeleton and one anionic -SO 3 - group, and is therefore electrically stable. Therefore, even if it is dispersed in a solvent, it is presumed that it does not dissociate and is excellent in stability. In addition, since the nitrogen atom has an aromatic substituent such as an aryl group or a heteroaryl group, the lone electron pair possessed by the nitrogen atom resonates not only with the dibenzopyran skeleton, but also with the aryl or heteroaryl group , it is presumed that the molecule is more stable. Furthermore, since the nitrogen atom is not directly bonded to the hydrogen atom, the hydrogen atom will not be detached from the nitrogen atom and the coloring material will not be unstable. Based on the above, the dibenzopyran-based dye represented by the general formula (3) is stable even under light irradiation and has excellent light resistance, and by using this colorant, a colored layer with excellent light resistance can be formed. In addition, fading of the colorant is suppressed, and as a result, the brightness of the colored layer can be improved. In addition, with respect to the dibenzopyran-based dye represented by the above general formula (3), R 3 and R 4 can be set to be different from each other, so that the range of molecular design is wide, and the adjustment range of spectroscopic properties and the like is also wide. , so it is easy to make the color material close to the target chromaticity, and then it is easy to improve the brightness. In addition, the dibenzopyran-based dye represented by the general formula (3) has a cationic dibenzopyran skeleton and only one anionic -SO 3 - group, and only has an inner salt, so it does not have alkali metal ions. Thereby, when the coloring layer is formed by using the dibenzopyran-based dye represented by the general formula (3), the elution of alkali metal ions from the coloring layer to the liquid crystal layer can be suppressed when a liquid crystal panel is produced, so that it is possible to A colored layer excellent in electrical reliability is obtained. Furthermore, the dibenzopyran-based dye represented by the general formula (3) has only one functional group containing SO 2 , so it is lower than PGMEA (Propylene Glycol Monomethyl Ether Acetate, propylene glycol monomethyl ether acetate) and the like. The affinity of polar solvents becomes high. Moreover, when dissolving the dibenzopyran-type dye represented by the said general formula (3) in a solvent, since a relatively low polarity solvent can be used, the stability of the photosensitive colored resin composition can be improved.

於上述通式(3)中,R 1及R 2中之烷基並無特別限定,例如可列舉可具有取代基之碳數1~20之直鏈或支鏈之烷基等,其中,較佳為碳數為1~8之直鏈或支鏈之烷基,更佳為碳數為1~5之直鏈或支鏈之烷基。作為烷基可具有之取代基,並無特別限定,例如可列舉:鹵素原子、芳基、胺甲醯基、-CO-O-R a所表示之一價基、-O-CO-R a'所表示之一價基、-SO 2-R a '所表示之一價基、-R b-CO-O-R c所表示之一價基、-R b'-O-CO-R c'所表示之一價基、及-R b '-SO 2-R c '所表示之一價基等。 R 1~R 4中之芳基並無特別限定,例如可列舉可具有取代基之碳數6~20之芳基,其中,較佳為具有苯基、萘基等之基。 R 3及R 4中之雜芳基並無特別限定,可列舉可具有取代基之碳數5~20之雜芳基,較佳為例如包含氮原子、氧原子、硫原子作為雜原子者。又,作為雜芳基,具體而言,例如可列舉呋喃、噻吩、吡咯、吡啶等。 作為芳基或雜芳基可具有之取代基,並無特別限定,例如可列舉:烷基、鹵素原子、烷氧基、羥基、胺甲醯基、-CO-O-R a所表示之一價基、-O-CO-R a'所表示之一價基、-SO 2-R a '所表示之一價基、-R b-CO-O-R c所表示之一價基、-R b'-O-CO-R c'所表示之一價基、-R b '-SO 2-R c '所表示之一價基等。 上述R a、R a'、R a "、R c、R c'及R c "表示烷基,上述R b、R b'及R b "表示伸烷基。該等取代基不會對耐熱性等造成不良影響,就該方面而言可較佳地使用。藉由調整基於該等取代基之吸電子性及供電子性,可調整分光特性。 再者,R 1~R 4中之烷基較佳為未經取代或取代基為芳基,芳基或雜芳基之取代基較佳為烷基。於此種情形時,上述通式(3)所表示之二苯并哌喃系染料之極性降低,因此與PGMEA等低極性溶劑之親和性提高。又,於使上述通式(3)所表示之二苯并哌喃系染料溶解於溶劑中時,亦可使用極性更低之低極性溶劑,藉由使用低極性溶劑,感光性著色樹脂組合物之穩定性提高。 又,R 1~R 4可分別相同,亦可不同,上述通式(3)所表示之二苯并哌喃系染料之R 1~R 4可相對於二苯并哌喃環對稱,亦可不對稱。其中,於使R 3及R 4彼此不同之情形時,上述通式(3)所表示之二苯并哌喃系染料之分子設計之範圍廣泛,分光特性之調整範圍亦變得廣泛,因此容易使該色料接近目標色度,進而容易提高亮度,就該方面而言較佳。 又,於上述通式(3)中,關於鍵結於二苯并哌喃骨架之苯環所具有之-SO 3 -基之取代位置,並無特別限定,較佳為相對於二苯并哌喃骨架為鄰位或對位,就耐熱性與耐光性之觀點而言,較佳為-SO 3 -基相對於二苯并哌喃骨架於鄰位上進行取代。其作用機制雖並不明確,但推定如下:若-SO 3 -基處於鄰位,則可與苯環所鍵結之二苯并哌喃骨架之碳原子進行共振而形成環結構,因此耐熱性與耐光性提高。 In the above general formula (3), the alkyl group in R 1 and R 2 is not particularly limited, for example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, etc. A straight-chain or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight-chain or branched alkyl group having 1 to 5 carbon atoms is more preferable. The substituent which the alkyl group may have is not particularly limited, and examples thereof include a halogen atom, an aryl group, an amine carboxyl group, a valent group represented by -CO-OR a , a valent group represented by -O-CO-R a' Represents a valent group, a valent group represented by -SO 2 -R a ' , a valent group represented by -R b -CO-OR c , a valent group represented by -R b' -O-CO-R c' A monovalent group, a monovalent group represented by -R b ' -SO 2 -R c ' , and the like. The aryl group in R 1 to R 4 is not particularly limited, and examples thereof include optionally substituted aryl groups having 6 to 20 carbon atoms, and among them, groups having a phenyl group, a naphthyl group, and the like are preferred. The heteroaryl group in R 3 and R 4 is not particularly limited, and examples thereof include optionally substituted heteroaryl groups having 5 to 20 carbon atoms, and preferably, for example, those containing a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. Moreover, as a heteroaryl group, a furan, a thiophene, a pyrrole, a pyridine etc. are mentioned specifically, for example. The substituent which the aryl group or the heteroaryl group may have is not particularly limited, and examples thereof include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, an amine carboxyl group, and a valent group represented by -CO-OR a . , a valent group represented by -O-CO-R a' , a valent group represented by -SO 2 -R a ' , a valent group represented by -R b -CO-OR c , -R b' - A valent group represented by O-CO-R c' , a valent group represented by -R b ' -SO 2 -R c ' , and the like. The above-mentioned R a , R a' , R a " , R c , R c' and R c " represent an alkyl group, and the above-mentioned R b , R b' and R b " represent an alkylene group. These substituents are not resistant to heat resistance In this respect, it can be used preferably. By adjusting the electron-withdrawing and electron-donating properties based on these substituents, the spectroscopic characteristics can be adjusted. Furthermore, the alkanes in R 1 to R 4 The group is preferably unsubstituted or the substituent is an aryl group, and the substituent of the aryl group or the heteroaryl group is preferably an alkyl group. In this case, the dibenzopyran represented by the general formula (3) is a The polarity of the dye is reduced, so the affinity with low-polarity solvents such as PGMEA is improved. Also, when the dibenzopyran-based dye represented by the above general formula (3) is dissolved in the solvent, a lower polarity can also be used. The use of a low-polarity solvent improves the stability of the photosensitive colored resin composition. In addition, R 1 to R 4 may be the same or different, respectively, and the dibenzophenone represented by the general formula (3) R 1 to R 4 of the pyran-based dye may be symmetric or asymmetric with respect to the dibenzopyran ring. Among them, when R 3 and R 4 are different from each other, the diphenyl group represented by the above general formula (3) The range of molecular design of the pyran-based dyes is wide, and the adjustment range of spectroscopic properties is also wide, so it is easy to make the colorant close to the target chromaticity, and it is easy to improve the brightness, which is preferable in this respect. In the general formula (3), the substitution position of the -SO 3 - group of the benzene ring bonded to the dibenzopyran skeleton is not particularly limited, but it is preferably an ortho-group relative to the dibenzopyran skeleton. Position or para position, from the viewpoint of heat resistance and light resistance, preferably -SO 3 - group is substituted at the ortho position with respect to the dibenzopyran skeleton. Although the mechanism of action is not clear, it is presumed as follows : When the -SO 3 - group is in the ortho position, it can resonate with the carbon atom of the dibenzopyran skeleton bonded to the benzene ring to form a ring structure, so the heat resistance and light resistance are improved.

又,上述通式(3)所表示之二苯并哌喃系染料可將-SO 3 -基轉化為-SO 3H基而使用。將-SO 3 -基轉化為-SO 3H基之方法並無特別限定。例如可列舉:利用弱酸游離反應之酸處理法、利用陽離子交換樹脂之方法等。 作為酸處理法,例如可列舉以下方法:使上述色料溶解於甲醇等良溶劑且可溶解酸之溶劑中,並添加酸,藉此將-SO 3 -基轉化為-SO 3H基。該酸處理法中所使用之酸只要為較將-SO 3 -基轉化為-SO 3H基之酸而言酸度更高之酸,便無特別限定。作為通用性較高之酸,例如可列舉:鹽酸、硫酸、硝酸、對甲苯磺酸(PTS)、三氟甲磺酸等。 另一方面,作為利用陽離子交換樹脂之方法中所使用之離子交換樹脂,可列舉Diaion PK-216H(三菱化學公司製造商品名)等磺酸末端之陽離子交換樹脂等。 再者,將色料之-SO 3 -基轉化為-SO 3H基之磺酸化處理係於使色料溶解於良溶劑中後進行,可不取出作為固體之具有磺基(-SO 3H)之色料,繼而於感光性著色樹脂組合物之製備、例如添加PGMEA或分散劑時進行。或者,亦可於進行色料之磺酸化後,藉由再沈澱法或再結晶法取出作為固體之具有磺基之色料後,製備感光性著色樹脂組合物。其中,就色料之回收率之觀點而言,較佳為前者之方法。 In addition, the dibenzopyran-based dye represented by the above-mentioned general formula (3) can be used by converting the -SO 3 - group into the -SO 3 H group. The method of converting the -SO 3 - group into the -SO 3 H group is not particularly limited. For example, the acid treatment method using weak acid liberation reaction, the method using a cation exchange resin, etc. are mentioned. The acid treatment method includes, for example, a method of converting the -SO 3 - group into a -SO 3 H group by dissolving the above colorant in a solvent such as methanol that dissolves an acid and adding an acid. The acid used in the acid treatment method is not particularly limited as long as it has a higher acidity than the acid for converting the -SO 3 - group into the -SO 3 H group. As an acid with high versatility, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid (PTS), trifluoromethanesulfonic acid, etc. are mentioned, for example. On the other hand, as an ion exchange resin used in the method using a cation exchange resin, the cation exchange resin of a sulfonic acid terminal, such as Diaion PK-216H (trade name made by Mitsubishi Chemical Corporation), etc. are mentioned. In addition, the sulfonation treatment of converting the -SO 3 - group of the colorant into the -SO 3 H group is performed after dissolving the color material in a good solvent, and the sulfo group (-SO 3 H) having a sulfo group (-SO 3 H) may not be taken out as a solid. The colorant is then carried out in the preparation of the photosensitive colored resin composition, for example, when PGMEA or a dispersant is added. Alternatively, after the sulfonation of the colorant, the photosensitive colored resin composition may be prepared by taking out the colorant having a sulfo group as a solid by a reprecipitation method or a recrystallization method. Among them, the former method is preferable from the viewpoint of the recovery rate of the colorant.

上述通式(3)所表示之二苯并哌喃系染料之製造方法並無特別限定,具體而言,例如可列舉下述方法。 使與磺基熒烷化合物對應之胺化合物於溶劑中進行回流,將該反應液於60℃下進行過濾而去除不溶解成分後,去除溶劑之一部分,注入至6%鹽酸中。繼而,加入大量水,於室溫下攪拌30分鐘後,過濾取出濕濾餅。利用水或熱水對該濕濾餅進行清洗後使其乾燥,藉此獲得上述通式(3)之色料。又,於製造R 1及R 3與R 2及R 4之一部分結構不同,相對於二苯并哌喃環而不對稱之通式(3)之色料時,將所對應之一半胺化合物逐次少量地滴加至充分稀釋之磺基熒烷化合物甲醇溶液中,於反應後滴加所剩之另一半胺化合物,或者將各胺化合物之1:1溶液緩慢地滴加至磺基熒烷化合物甲醇溶液中,藉此可以高產率獲得不對稱之通式(3)之色料。 再者,上述通式(3)所表示之二苯并哌喃系染料可單獨使用一種,亦可組合兩種以上而使用。 The manufacturing method of the dibenzopyran-type dye represented by the said General formula (3) is not specifically limited, Specifically, the following method is mentioned, for example. The amine compound corresponding to the sulfofluoran compound was refluxed in the solvent, and the reaction solution was filtered at 60° C. to remove insoluble components, and then a part of the solvent was removed and poured into 6% hydrochloric acid. Then, a large amount of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake is washed with water or hot water, and then dried to obtain the colorant of the general formula (3). In addition, when R 1 and R 3 and R 2 and R 4 have different partial structures and are asymmetric with respect to the dibenzopyran ring of the general formula (3), the corresponding half-amine compounds are successively A small amount was added dropwise to the fully diluted methanol solution of the sulfofluoran compound, and the remaining half amine compound was added dropwise after the reaction, or the 1:1 solution of each amine compound was slowly added dropwise to the sulfofluoran compound. In methanol solution, the asymmetric colorant of general formula (3) can be obtained in high yield. In addition, the dibenzopyran-type dye represented by the said General formula (3) may be used individually by 1 type, and may be used in combination of 2 or more types.

於本發明之感光性著色樹脂組合物中,藉由使用下述通式(4)所表示之二苯并哌喃系染料,可抑制異物之產生,從而可形成亮度得到提高之著色層。In the photosensitive colored resin composition of the present invention, by using the dibenzopyran-based dye represented by the following general formula (4), generation of foreign matter can be suppressed, and a colored layer with improved brightness can be formed.

[化10] 通式(4)

Figure 02_image023
(通式(4)中,R 5及R 6分別獨立地為可具有取代基之脂肪族烴基或芳香族烴基,R 7及R 8分別獨立地為可具有取代基之芳香族烴基或芳香族雜環基,R 7及R 8之至少1個芳香族烴基或芳香族雜環基經脂肪族烴基取代,R 7及R 8彼此不同;L 1及L 2分別獨立地為直接鍵、-SO 2-、或-CO-,R 9為鹵化脂肪族烴基) [Chemical 10] General formula (4)
Figure 02_image023
(In the general formula (4), R 5 and R 6 are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent, and R 7 and R 8 are each independently an aromatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent group. Heterocyclic group, at least one aromatic hydrocarbon group of R 7 and R 8 or aromatic heterocyclic group is substituted by aliphatic hydrocarbon group, R 7 and R 8 are different from each other; L 1 and L 2 are each independently a direct bond, -SO 2- , or -CO-, R 9 is halogenated aliphatic hydrocarbon group)

上述通式(4)所表示之二苯并哌喃系染料之特徵在於:除具有二苯并哌喃作為基本骨架以外,還僅具有1個特定之-L 1-N --L 2-R 9即包含陰離子部之官能基,與氮原子鍵結之R 5~R 8之任一者均非氫原子,R 7及R 8為芳香族烴基或芳香族雜環基,R 7及R 8之至少1個芳香族烴基或芳香族雜環基經脂肪族烴基取代,R 7及R 8彼此不同。藉由使用具有此種特徵之上述通式(4)所表示之二苯并哌喃系染料,可抑制異物之產生,可形成亮度得到提高之著色層,關於上述作用,雖有不明之處,但考慮如下。上述通式(4)所表示之二苯并哌喃系染料具有一價之陽離子性二苯并哌喃骨架、及1個陰離子性之-L 1-N --L 2-R 9基,僅具有內鹽,因此於1分子內在電性上變得穩定。另一方面,於陰離子性之-L 1-N --L 2-R 9基中,在R 9處鍵結有陰電性較高之鹵素,藉此陰離子部位之電子容易被吸引至R 9,陰離子性變弱,因此推定分子間之離子鍵變弱。又,上述通式(4)所表示之二苯并哌喃系染料係如下結構,即與氮原子鍵結之R 5~R 8之任一者均非氫原子,R 7及R 8為芳香族烴基或芳香族雜環基,R 7及R 8之至少1個經脂肪族烴基取代,R 7及R 8彼此不同,相對於二苯并哌喃骨架而不對稱,因此推定結晶性較低,不易凝聚,且溶劑親和性變高。自其等之協同效應而推定,上述通式(4)所表示之二苯并哌喃系染料之溶劑溶解性提高,於使用包含上述通式(4)所表示之二苯并哌喃系染料之著色樹脂組合物來形成著色層之情形時,可抑制異物之產生。 又,上述通式(4)所表示之二苯并哌喃系染料由於與二苯并哌喃骨架鍵結之氮原子未直接與氫原子鍵結,故而不會有氫原子自氮原子脫離而導致該色料不穩定之情況,由於氮原子具有如芳香族烴基或芳香族雜環基之芳香族性取代基,故而該氮原子所具有之孤電子對不僅與二苯并哌喃骨架,還與該芳香族烴基或芳香族雜環基進行共振,藉此上述通式(4)所表示之二苯并哌喃系染料具有穩定性較高之分子結構。上述通式(4)所表示之二苯并哌喃系染料如上所述具有穩定性較高之分子結構,因此耐熱性良好。 進而,上述通式(4)所表示之二苯并哌喃系染料中,由於R 7及R 8之至少1個芳香族烴基或芳香族雜環基經脂肪族烴基取代,R 7及R 8彼此不同,故而染料彼此不易凝聚,且由於溶劑溶解性較高,故而亦不易產生異物,因此亦不會使著色層之透光量衰減。 又,上述通式(4)所表示之二苯并哌喃系染料中,R 7及R 8彼此不同,分子設計之範圍廣泛,因此分光特性等之調整範圍亦廣泛,因此容易使該色料接近目標色度,進而容易提高亮度。 如上所述,若使用上述通式(4)所表示之二苯并哌喃系染料,則可推定如下:由於耐熱性良好,故而抑制彩色濾光片製造步驟之烘烤後之亮度降低,於彩色濾光片製造步驟中抑制染料之凝聚及異物之產生,可根據所需色度來設計結構而調整分光特性等,藉此亦可提高著色層之亮度。 The dibenzopyran-based dye represented by the general formula (4) is characterized by having only one specific -L 1 -N - -L 2 -R in addition to having dibenzopyran as a basic skeleton 9 is a functional group including an anion moiety, any of R 5 to R 8 bonded to a nitrogen atom is not a hydrogen atom, R 7 and R 8 are aromatic hydrocarbon groups or aromatic heterocyclic groups, R 7 and R 8 At least one aromatic hydrocarbon group or aromatic heterocyclic group is substituted with an aliphatic hydrocarbon group, and R 7 and R 8 are different from each other. By using the dibenzopyran-based dye represented by the above-mentioned general formula (4) having such characteristics, the generation of foreign matter can be suppressed, and a colored layer with improved brightness can be formed. But consider the following. The dibenzopyran-based dye represented by the general formula (4) has a monovalent cationic dibenzopyran skeleton and an anionic -L 1 -N - -L 2 -R 9 group, and only Since it has an inner salt, it becomes electrically stable within 1 molecule. On the other hand, in the anionic -L 1 -N - -L 2 -R 9 group, a halogen with a higher negative charge is bonded at R 9 , whereby the electrons in the anion site are easily attracted to R 9 , the anionicity becomes weaker, so it is presumed that the ionic bond between the molecules becomes weaker. In addition, the dibenzopyran-based dye represented by the general formula (4) has a structure in which any of R 5 to R 8 bonded to a nitrogen atom is not a hydrogen atom, and R 7 and R 8 are aromatic An aliphatic hydrocarbon group or an aromatic heterocyclic group, at least one of R 7 and R 8 is substituted with an aliphatic hydrocarbon group, R 7 and R 8 are different from each other, and are asymmetric with respect to the dibenzopyran skeleton, so it is presumed that the crystallinity is low , it is not easy to agglomerate, and the solvent affinity becomes higher. From the synergistic effect thereof, it is presumed that the solvent solubility of the dibenzopyran-based dye represented by the above general formula (4) is improved, and the use of the dibenzopyran-based dye containing the above-mentioned general formula (4) is presumed. When the coloring resin composition is used to form a coloring layer, the generation of foreign matter can be suppressed. In addition, the dibenzopyran-based dye represented by the above-mentioned general formula (4) is not directly bonded to a hydrogen atom because the nitrogen atom bonded to the dibenzopyran skeleton does not detach a hydrogen atom from the nitrogen atom. In the case of the instability of the colorant, since the nitrogen atom has an aromatic substituent such as an aromatic hydrocarbon group or an aromatic heterocyclic group, the lone electron pair possessed by the nitrogen atom is not only related to the dibenzopyran skeleton, but also By resonating with the aromatic hydrocarbon group or the aromatic heterocyclic group, the dibenzopyran-based dye represented by the general formula (4) has a highly stable molecular structure. The dibenzopyran-based dye represented by the above-mentioned general formula (4) has a highly stable molecular structure as described above, and thus has good heat resistance. Furthermore, in the dibenzopyran-based dye represented by the general formula (4), since at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is substituted with an aliphatic hydrocarbon group, R 7 and R 8 Since the dyes are different from each other, the dyes are not easily agglomerated with each other, and since the solvent solubility is high, foreign matter is not easily generated, so the light transmittance of the colored layer is not attenuated. In addition, in the dibenzopyran-based dye represented by the above general formula (4), R 7 and R 8 are different from each other, and the range of molecular design is wide, so the adjustment range of spectral characteristics and the like is also wide, so it is easy to make the dye Approaching the target chromaticity, it is easy to increase the brightness. As described above, when the dibenzopyran-based dye represented by the above-mentioned general formula (4) is used, it can be presumed that the reduction in luminance after baking in the color filter manufacturing step is suppressed due to good heat resistance, and the In the color filter manufacturing process, the agglomeration of dyes and the generation of foreign matter can be suppressed, the structure can be designed according to the required chromaticity, and the spectroscopic properties can be adjusted, thereby improving the brightness of the coloring layer.

上述通式(4)中,R 5及R 6中之脂肪族烴基可為直鏈狀、支鏈狀、環狀之任一者,並無特別限定,例如可列舉碳數1以上20以下之直鏈或支鏈狀脂肪族烴基、或者碳數5以上8以下之環狀脂肪族烴基(脂環式烴基)等,就耐熱性之觀點而言,較佳為碳數為10以下。作為脂肪族烴基,較佳為作為飽和脂肪族烴基之直鏈狀、支鏈狀、環狀之烷基。 作為該脂肪族烴基可具有之取代基,並無特別限定,例如可列舉:鹵素原子、芳香族烴基、胺甲醯基、-CO-O-R d所表示之一價基、-O-CO-R d'所表示之一價基、-SO 2-R d "所表示之一價基、-R e-CO-O-R f所表示之一價基、-R e'-O-CO-R f'所表示之一價基、及-R e "-SO 2-R f "所表示之一價基等。 R 5~R 8中之芳香族烴基並無特別限定,例如可列舉可具有取代基之碳數6以上20以下之芳香族烴基,其中較佳為具有苯基、萘基等之基。 R 7及R 8中之芳香族雜環基並無特別限定,可列舉可具有取代基之碳數5以上20以下之芳香族雜環基,較佳為例如包含氮原子、氧原子、硫原子作為雜原子者。又,作為芳香族雜環基,具體而言,例如可列舉呋喃、噻吩、吡咯、吡啶等。 作為芳香族烴基或芳香族雜環基可具有之取代基,並無特別限定,例如可列舉:脂肪族烴基、鹵素原子、烷氧基、羥基、胺甲醯基、-CO-O-R d所表示之一價基、-O-CO-R d'所表示之一價基、-SO 2-R d "所表示之一價基、-R e-CO-O-R f所表示之一價基、-R e'-O-CO-R f'所表示之一價基、-R e '-SO 2-R f "所表示之一價基等。上述R e、R e'、R e "、R d、R d'、R d "、R f、R f'及R f "表示脂肪族烴基。該等取代基不會對耐熱性等造成不良影響,就該方面而言可較佳地使用。藉由調整基於該等取代基之吸電子性及供電子性,可調整分光特性。又,此處之脂肪族烴基可與R 5及R 6中之脂肪族烴基相同。 In the above general formula (4), the aliphatic hydrocarbon group in R 5 and R 6 may be any of linear, branched, and cyclic, and is not particularly limited, and examples thereof include 1 to 20 carbon atoms. The linear or branched aliphatic hydrocarbon group, or the cyclic aliphatic hydrocarbon group (alicyclic hydrocarbon group) having 5 to 8 carbon atoms (alicyclic hydrocarbon group), etc., preferably has 10 or less carbon atoms from the viewpoint of heat resistance. The aliphatic hydrocarbon group is preferably a linear, branched or cyclic alkyl group which is a saturated aliphatic hydrocarbon group. The substituent which the aliphatic hydrocarbon group may have is not particularly limited, and examples thereof include a halogen atom, an aromatic hydrocarbon group, an amine carboxyl group, a valent group represented by -CO-OR d , -O-CO-R A valent group represented by d' , a valent group represented by -SO 2 -R d " , a valent group represented by -R e -CO-OR f , -R e' -O-CO-R f' A valent group represented by -R e " -SO 2 -R f " , and the like. The aromatic hydrocarbon group in R 5 to R 8 is not particularly limited, and examples thereof include those which may have a substituent. Aromatic hydrocarbon groups having 6 or more carbon atoms and 20 or less carbon atoms, preferably a group having a phenyl group, a naphthyl group, etc. The aromatic heterocyclic groups in R 7 and R 8 are not particularly limited, and may include carbon atoms which may have a substituent The aromatic heterocyclic group having a number of 5 or more and 20 or less is preferably, for example, one containing a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom. As the aromatic heterocyclic group, for example, furan, thiophene, Pyrrole, pyridine, etc. The substituent which the aromatic hydrocarbon group or the aromatic heterocyclic group may have is not particularly limited, and examples thereof include aliphatic hydrocarbon group, halogen atom, alkoxy group, hydroxyl group, carbamoyl group, -CO A valence group represented by -OR d , a valence group represented by -O-CO-R d' , a valence group represented by -SO 2 -R d " , a valence group represented by -R e -CO-OR f A monovalent group, a valent group represented by -R e' -O-CO-R f' , a valent group represented by -R e ' -SO 2 -R f " , etc. The above-mentioned Re , Re ' , R e " , R d , R d' , R d " , R f , R f' and R f " represent aliphatic hydrocarbon groups. These substituents do not adversely affect heat resistance and the like, and can be preferably used in this respect. Spectroscopic properties can be adjusted by adjusting the electron-withdrawing properties and electron-donating properties based on these substituents. In addition, the aliphatic hydrocarbon group here may be the same as the aliphatic hydrocarbon group in R 5 and R 6 .

就可抑制異物之產生,容易形成亮度得到提高之著色層之觀點而言,較佳為R 5及R 6之至少1個為脂肪族烴基,較佳為R 5及R 6為脂肪族烴基,其中較佳為直鏈脂肪族烴基。作為該脂肪族烴基,較佳為碳數1以上10以下,進而較佳為碳數1以上6以下之直鏈烷基。 就可抑制異物之產生,容易形成亮度得到提高之著色層之觀點而言,較佳為R 7及R 8之至少1個為芳香族烴基,較佳為R 7及R 8為芳香族烴基。作為該芳香族烴基,較佳為碳數6以上10以下之芳香族烴基,進而較佳為苯基。 又,作為可具有取代基之芳香族烴基或芳香族雜環基之R 7及R 8之至少1個經脂肪族烴基取代,R 7及R 8彼此不同。 作為與該芳香族烴基或芳香族雜環基之氫原子進行了取代之脂肪族烴基,其中較佳為直鏈脂肪族烴基。作為該脂肪族烴基,較佳為碳數1以上10以下,進而較佳為碳數1以上6以下之直鏈烷基。又,較佳為R 7及R 8兩者均經如上所述之脂肪族烴基取代。 又,就可抑制異物之產生,容易形成亮度得到提高之著色層之觀點而言,R 7及R 8之至少1個芳香族烴基或芳香族雜環基較佳為每1個芳香族烴基或芳香族雜環基經2個以上之脂肪族烴基取代。 又,於R 5、R 6、R 7及R 8中所含之脂肪族烴基之任一個為碳數2以上、進而為碳數3以上之直鏈烷基之情形時,呈容易調整分子中之電子密度之趨勢。 於R 5及R 6之至少1個經直鏈肪族烴基取代,且R 7及R 8之至少1個芳香族烴基或芳香族雜環基經碳數2以上之直鏈烷基取代之情形時,容易抑制異物之產生,從而容易形成亮度得到提高之著色層。 From the viewpoint of suppressing the generation of foreign matter and easily forming a colored layer with improved brightness, at least one of R 5 and R 6 is preferably an aliphatic hydrocarbon group, preferably R 5 and R 6 are aliphatic hydrocarbon groups, Of these, straight-chain aliphatic hydrocarbon groups are preferred. The aliphatic hydrocarbon group is preferably a linear alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. From the viewpoint of suppressing the generation of foreign matter and easily forming a colored layer with improved brightness, at least one of R 7 and R 8 is preferably an aromatic hydrocarbon group, and preferably R 7 and R 8 are an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group. In addition, at least one of R 7 and R 8 of the optionally substituted aromatic hydrocarbon group or the aromatic heterocyclic group is substituted with an aliphatic hydrocarbon group, and R 7 and R 8 are different from each other. As the aliphatic hydrocarbon group substituted with the hydrogen atom of the aromatic hydrocarbon group or the aromatic heterocyclic group, a straight-chain aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group is preferably a linear alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, and more preferably a linear alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Also, it is preferable that both of R 7 and R 8 are substituted with aliphatic hydrocarbon groups as described above. In addition, from the viewpoint of suppressing the generation of foreign matter and easily forming a coloring layer with improved brightness, at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is preferably every aromatic hydrocarbon group or The aromatic heterocyclic group is substituted with two or more aliphatic hydrocarbon groups. In addition, when any one of the aliphatic hydrocarbon groups contained in R 5 , R 6 , R 7 and R 8 is a straight-chain alkyl group having 2 or more carbon atoms, and furthermore, a straight-chain alkyl group having 3 or more carbon atoms, it is easy to adjust the molecular weight. trends in electron density. In the case where at least one of R 5 and R 6 is substituted with a straight-chain aliphatic hydrocarbon group, and at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is substituted with a straight-chain alkyl group having 2 or more carbon atoms In this case, it is easy to suppress the generation of foreign matter, so that it is easy to form a coloring layer with improved brightness.

又,R 5~R 8中,脂肪族烴基較佳為未經取代,或者於其為支鏈狀或直鏈狀之烷基之情形時取代基為芳香族烴基,芳香族烴基或芳香族雜環基之取代基較佳為脂肪族烴基。其原因在於:於此種情形時,上述通式(4)所表示之二苯并哌喃系染料之極性降低,因此與PGMEA等低極性溶劑之親和性提高。又,於使上述色料溶解於溶劑中時,亦可使用極性更低之低極性溶劑,藉由使用低極性溶劑,使得本發明之感光性著色樹脂組合物之穩定性提高。其中,就與低極性溶劑之親和性提高之觀點而言,作為芳香族烴基或芳香族雜環基之取代基,較佳為僅具有脂肪族烴基。 In addition, among R 5 to R 8 , the aliphatic hydrocarbon group is preferably unsubstituted, or when it is a branched or straight-chain alkyl group, the substituent is an aromatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic heterocyclic group. The substituent of the cyclic group is preferably an aliphatic hydrocarbon group. The reason for this is that in this case, the polarity of the dibenzopyran-based dye represented by the general formula (4) is lowered, so that the affinity with low-polarity solvents such as PGMEA is improved. Moreover, when dissolving the said coloring material in a solvent, the low polarity solvent with lower polarity can also be used, and the stability of the photosensitive colored resin composition of this invention can be improved by using a low polarity solvent. Among these, it is preferable to have only aliphatic hydrocarbon group as a substituent of an aromatic hydrocarbon group or an aromatic heterocyclic group from a viewpoint of improving the affinity with a low polar solvent.

-L 1-N --L 2-R 9基中之L 1及L 2分別獨立地為直接鍵、-SO 2-、或-CO-,其中較佳為-SO 2-、或-CO-,進而,就可抑制異物之產生,容易形成耐熱性優異且亮度得到提高之著色層之觀點而言,較佳為-SO 2-。 L 1 and L 2 in the -L 1 -N - -L 2 -R 9 group are each independently a direct bond, -SO 2 -, or -CO-, and preferably -SO 2 - or -CO- Furthermore, -SO 2 - is preferable from the viewpoint of suppressing the generation of foreign matter and easily forming a coloring layer having excellent heat resistance and improved brightness.

-L 1-N --L 2-R 9基中之R 9為鹵化脂肪族烴基,作為該鹵素,可列舉氟原子、氯原子、碘原子等,其中較佳為氟原子。作為R 9之鹵化脂肪族烴基,較佳為碳數為1以上8以下之直鏈或支鏈之鹵化脂肪族烴基,更佳為碳數為1以上5以下之直鏈或支鏈之鹵化脂肪族烴基,進而更佳為碳數為1以上3以下之直鏈或支鏈之鹵化脂肪族烴基。其中,脂肪族烴基中之鹵素原子之取代率(鹵素原子數/脂肪族烴基之氫原子之總數)較佳為50%以上,進而較佳為70%以上,其中較佳為100%。 作為R 9,其中較佳為碳數為1以上5以下之直鏈或支鏈之全氟烷基。 R 9 in the -L 1 -N - -L 2 -R 9 group is a halogenated aliphatic hydrocarbon group, and examples of the halogen include a fluorine atom, a chlorine atom, an iodine atom, and the like, among which a fluorine atom is preferred. The halogenated aliphatic hydrocarbon group for R 9 is preferably a linear or branched halogenated aliphatic hydrocarbon group with 1 to 8 carbon atoms, more preferably a linear or branched halogenated aliphatic group with 1 to 5 carbon atoms. A hydrocarbon group, more preferably a linear or branched halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms. The substitution ratio of halogen atoms in the aliphatic hydrocarbon group (number of halogen atoms/total number of hydrogen atoms in the aliphatic hydrocarbon group) is preferably 50% or more, more preferably 70% or more, and more preferably 100%. Among them, R 9 is preferably a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms.

又,上述通式(4)中,關於鍵結於二苯并哌喃骨架之苯環所具有之-L 1-N --L 2-R 9基之取代位置,並無特別限定,較佳為相對於二苯并哌喃骨架為鄰位或對位,就上述通式(4)所表示之二苯并哌喃系染料之各種耐受性之觀點而言,較佳為-L 1-N --L 2-R 9基相對於二苯并哌喃骨架被取代至鄰位。其作用機制雖不明確,但推定如下:若-L 1-N --L 2-R 9基處於鄰位,則可與鍵結有苯環之二苯并哌喃骨架之碳原子進行共振而形成環結構,分子之穩定性變高,因此色料之各種耐受性提高。 In addition, in the above general formula (4), the substitution position of the -L 1 -N - -L 2 -R 9 group of the benzene ring bonded to the dibenzopyran skeleton is not particularly limited, but is preferably In order to be in the ortho position or the para position with respect to the dibenzopyran skeleton, from the viewpoint of various tolerances of the dibenzopyran-based dye represented by the general formula (4), -L 1 - is preferred. The N - -L 2 -R 9 group is substituted to the ortho position with respect to the dibenzopyran skeleton. Although its mechanism of action is not clear, it is presumed as follows: if the -L 1 -N - -L 2 -R 9 group is in the ortho position, it can resonate with the carbon atom of the dibenzopyran skeleton to which the benzene ring is bonded. A ring structure is formed, and the stability of the molecule becomes high, so that the various tolerances of the colorant are improved.

關於上述通式(4)所表示之二苯并哌喃系染料之製造方法,並無特別限定,具體而言,例如可列舉下述方法。 使磺基熒烷化合物及與R 7及R 8對應之胺化合物於溶劑中以60℃進行回流,將該反應液於60℃下進行過濾而去除不溶解成分後,去除溶劑之一部分,注入至6%鹽酸中。繼而,加入大量水,於室溫下攪拌30分鐘後,過濾取出濕濾餅。利用水或熱水對該濕濾餅進行清洗後使其乾燥,藉此可獲得上述通式(4)所表示之色素之中間物。再者,於本發明中,為了製造R 7及R 8之一部分結構不同,相對於二苯并哌喃環而不對稱之通式(4)之色素,而將所對應之一半胺化合物逐次少量地滴加至充分稀釋之磺基熒烷化合物甲醇溶液中,反應後滴加所剩之另一半胺化合物,或者將各胺化合物之1:1溶液緩慢地滴加至磺基熒烷化合物甲醇溶液中,藉此可以高產率獲得不對稱之通式(4)所表示之色素之中間物。 繼而,於1-甲基-2-吡咯啶酮等極性溶劑中,在存在碳酸鉀等鹼之情況下,將通式(4)所表示之色素之中間物、及與R 5及R 6對應之鹵化物於80℃下攪拌2小時而進行反應。反應結束後,將反應溶液放冷至室溫後,將反應溶液滴加至0~10℃之17.5%鹽酸中,攪拌1小時。然後,過濾取出析出物,使殘渣於60℃下乾燥24小時,藉此獲得通式(4)所表示之色素之前驅物。 繼而,使不對稱之通式(4)之色料之前驅物及三氟甲基磺醯胺溶解於氯仿中,滴加三乙胺而進行反應。然後,對所獲得之反應溶液進行水洗,繼而分取有機層。利用硫酸鈉使該有機層乾燥,藉由管柱層析法進行精製,進行減壓濃縮,藉此可獲得上述通式(4)所表示之二苯并哌喃系染料。 又,於L 1由-CO-表示之情形時,可使用熒烷化合物代替磺基熒烷化合物,除此以外均同樣地進行而獲得上述通式(4)所表示之二苯并哌喃系染料。 Although it does not specifically limit about the manufacturing method of the dibenzopyran-type dye represented by the said General formula (4), For example, the following method is mentioned. The sulfofluoran compound and the amine compound corresponding to R 7 and R 8 were refluxed in a solvent at 60°C, and the reaction solution was filtered at 60°C to remove insoluble components, and then a part of the solvent was removed and injected into 6% hydrochloric acid. Then, a large amount of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake is washed with water or hot water, and then dried, whereby the intermediate of the pigment represented by the above-mentioned general formula (4) can be obtained. Furthermore, in the present invention, in order to produce a pigment of the general formula (4) that is asymmetric with respect to the dibenzopyran ring, a part of the structure of R 7 and R 8 is different, and a small amount of the corresponding hemiamine compound is successively used. Add dropwise to the fully diluted methanol solution of sulfofluoran compound, after the reaction, add the remaining half amine compound dropwise, or slowly add the 1:1 solution of each amine compound dropwise to the methanol solution of sulfofluoran compound In this way, an asymmetric intermediate of the pigment represented by the general formula (4) can be obtained in high yield. Next, in a polar solvent such as 1-methyl-2-pyrrolidone, in the presence of a base such as potassium carbonate, the intermediate of the dye represented by the general formula (4), and R 5 and R 6 correspond to The halide was stirred at 80°C for 2 hours to carry out the reaction. After the reaction was completed, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 17.5% hydrochloric acid at 0 to 10° C. and stirred for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60° C. for 24 hours to obtain a dye precursor represented by the general formula (4). Next, the color precursor of the asymmetric general formula (4) and trifluoromethylsulfonamide were dissolved in chloroform, and triethylamine was added dropwise to conduct the reaction. Then, the obtained reaction solution was washed with water, and then the organic layer was separated. The organic layer is dried with sodium sulfate, purified by column chromatography, and concentrated under reduced pressure, whereby the dibenzopyran-based dye represented by the above-mentioned general formula (4) can be obtained. In addition, when L 1 is represented by -CO-, a fluoran compound can be used in place of the sulfofluoran compound, and the dibenzopyran system represented by the above-mentioned general formula (4) can be obtained in the same manner. dye.

上述通式(4)所表示之二苯并哌喃系染料對於低極性溶劑而言亦溶劑溶解性高,因此即便不使用具有醇性羥基之溶劑,亦具有著色層用途所需之濃度下之溶劑溶解性。上述通式(4)所表示之二苯并哌喃系染料較佳為,相對於丙二醇單甲醚乙酸酯、乙酸-3-甲氧基-3-甲基-1-丁酯、及二乙二醇乙基甲醚之至少一者,23℃下之上述通式(4)所表示之二苯并哌喃系染料之溶解度為2.0(g/100 g溶劑)以上,更佳為2.5(g/100 g溶劑)以上。 再者,上述通式(4)所表示之二苯并哌喃系染料可單獨使用一種,亦可組合兩種以上而使用。 The dibenzopyran-based dye represented by the general formula (4) has high solvent solubility in low-polarity solvents, so even if a solvent having an alcoholic hydroxyl group is not used, it has a concentration required for the coloring layer application. Solvent solubility. The dibenzopyran-based dyes represented by the general formula (4) are preferably propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, and At least one of ethylene glycol ethyl methyl ether, the solubility of the dibenzopyran-based dye represented by the above general formula (4) at 23°C is 2.0 (g/100 g solvent) or more, more preferably 2.5 ( g/100 g solvent) or more. In addition, the dibenzopyran-type dye represented by the said general formula (4) may be used individually by 1 type, and may be used in combination of 2 or more types.

(二苯并哌喃系染料之色澱色料) 作為與上述通式(1)或通式(2)所表示之色澱色料組合而使用之二苯并哌喃系染料之色澱色料,並無特別限定,例如可使用與上述通式(1)或通式(2)所表示之色澱色料不同之公知之二苯并哌喃系染料之色澱色料。其中,就色料之耐熱性及分散性優異,可獲得高亮度之著色層之觀點而言,可較佳地使用以包含金屬原子之色澱化劑使二苯并哌喃系染料色澱化而成之二苯并哌喃系染料之金屬色澱色料。再者,金屬色澱色料係加成有作為色澱化劑之金屬之色澱色料。 (Lake color of dibenzopyran dyes) It does not specifically limit as the lake coloring material of the dibenzopyran-based dye used in combination with the lake coloring material represented by the above-mentioned general formula (1) or the general formula (2), for example, the same as the above-mentioned general formula can be used. (1) The lake coloring material of a known dibenzopyran-based dye which is different from the lake coloring material represented by the general formula (2). Among them, from the viewpoint of being excellent in heat resistance and dispersibility of the colorant and obtaining a high-brightness colored layer, a lake-forming agent containing a metal atom can be preferably used to lake a dibenzopyran-based dye. It is the metallic lake color of the dibenzopyran series dyes. Furthermore, the metallic lake coloring material is a metallic lake coloring material added as a lake-forming agent.

作為與上述通式(1)或通式(2)所表示之色澱色料不同之二苯并哌喃系染料之色澱色料,其中,較佳為於二苯并哌喃骨架之9位具有苯基之二苯并哌喃系染料之色澱色料。具體而言,可較佳地使用以色澱化劑使下述通式(5)所表示之二苯并哌喃系染料色澱化而成之色澱色料,尤其可較佳地使用以包含金屬原子之色澱化劑使下述通式(5)所表示之二苯并哌喃系染料色澱化而成之金屬色澱色料。As the lake coloring material of the dibenzopyran-based dye different from the lake coloring material represented by the general formula (1) or the general formula (2), among them, 9 in the dibenzopyran skeleton is preferred. It is a lake color of dibenzopyran-based dyes with a phenyl group in the position. Specifically, a lake coloring material obtained by lakeing a dibenzopyran-based dye represented by the following general formula (5) with a lake-forming agent can be preferably used, especially A metal lake coloring material obtained by lake-forming a dibenzopyran-based dye represented by the following general formula (5) with a lake-forming agent containing a metal atom.

[化11] 通式(5)

Figure 02_image025
(通式(5)中,R 1'、R 2'、R 3'及R 4'分別獨立地表示氫原子、烷基、芳基、或雜芳基,R 1'與R 3'、R 2'與R 4'分別可鍵結而形成環結構,R 1'與二苯并哌喃環之5位碳原子、R 3'與二苯并哌喃環之7位碳原子、R 2'與二苯并哌喃環之4位碳原子、或R 4'與二苯并哌喃環之2位碳原子分別可鍵結而形成環結構;上述芳基、或雜芳基所具有之氫原子可經酸性基或其鹽、或者鹵素原子取代;R 5'表示酸性基或其鹽,x為0~5之整數;其中,通式(5)具有至少2個酸性基或其鹽,且其中1個形成內鹽) [Chem. 11] General formula (5)
Figure 02_image025
(In general formula (5), R 1' , R 2' , R 3' and R 4' each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, R 1' and R 3' , R 2' and R 4' can be bonded respectively to form a ring structure, R 1' and the 5th carbon atom of the dibenzopyran ring, R 3' and the 7th carbon atom of the dibenzopyran ring, R 2' It can be bonded to the 4-position carbon atom of the dibenzopyran ring, or R 4' and the 2-position carbon atom of the dibenzopyran ring, respectively, to form a ring structure; the hydrogen possessed by the above-mentioned aryl group or heteroaryl group The atom may be substituted by an acidic group or a salt thereof, or a halogen atom; R 5' represents an acidic group or a salt thereof, and x is an integer of 0 to 5; wherein, the general formula (5) has at least 2 acidic groups or a salt thereof, and 1 of which forms an inner salt)

關於R 1'~R 4'中之烷基,其中較佳為可具有取代基之碳數1~20之直鏈或支鏈狀烷基,更佳為碳數為1~8之直鏈或支鏈之烷基,進而更佳為碳數為1~5之直鏈或支鏈之烷基。作為烷基可具有之取代基,並無特別限定,例如可列舉芳基、鹵素原子等,該芳基可進而具有鹵素原子、或者酸性基或其鹽作為取代基。 關於R 1'~R 4'中之芳基,其中較佳為碳數6~20之可具有取代基之芳基,更佳為具有苯基、萘基等之基。 又,關於R 1'~R 4'中之雜芳基,其中較佳為碳數5~20之可具有取代基之雜芳基,較佳為包含氮原子、氧原子、硫原子作為雜原子者。 作為芳基或雜芳基可具有之取代基,例如可列舉:碳數1~5之烷基、鹵素原子、酸性基或其鹽、羥基、烷氧基、腈基、胺甲醯基、羧酸酯基等。 As for the alkyl group in R 1' to R 4' , among them, a straight-chain or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferable, and a straight-chain or branched alkyl group having 1 to 8 carbon atoms is more preferable. The branched-chain alkyl group is more preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Although it does not specifically limit as a substituent which an alkyl group may have, For example, an aryl group, a halogen atom etc. are mentioned, This aryl group may further have a halogen atom, or an acidic group or its salt as a substituent. Among the aryl groups in R 1' to R 4' , preferably aryl groups having 6 to 20 carbon atoms which may have a substituent, and more preferably groups having a phenyl group, a naphthyl group, or the like. In addition, as for the heteroaryl group in R 1' to R 4' , among them, preferably a heteroaryl group having 5 to 20 carbon atoms which may have a substituent, and preferably one containing nitrogen atom, oxygen atom, and sulfur atom as hetero atoms By. Examples of the substituent which the aryl group or the heteroaryl group may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group or a salt thereof, a hydroxyl group, an alkoxy group, a nitrile group, an amine carboxyl group, and a carboxyl group. Acid group, etc.

所謂R 1'與R 3'、R 2'與R 4'分別鍵結而形成了環結構,意指R 1'與R 3'、R 2'與R 4'分別經由氮原子而形成環結構。環結構並無特別限定,例如可列舉5~7員環之含氮雜環,具體而言可列舉吡咯啶環、哌啶環、𠰌啉環等。 又,所謂R 1'與二苯并哌喃環之5位碳原子、R 3'與二苯并哌喃環之7位碳原子、R 2'與二苯并哌喃環之4位碳原子、或R 4'與二苯并哌喃環之2位碳原子鍵結而形成了環結構,意指R 1'~R 4'、與二苯并哌喃環之規定位之碳原子之上述組合分別經由氮原子及二苯并哌喃骨架之一部分而形成了環結構。環結構並無特別限定,例如可列舉5~7員環之含氮雜環。 The fact that R 1' and R 3' , and R 2' and R 4' are respectively bonded to form a ring structure means that R 1' and R 3' , and R 2' and R 4' respectively form a ring structure through a nitrogen atom. . The ring structure is not particularly limited, and examples thereof include nitrogen-containing heterocycles having 5 to 7 members, and specific examples thereof include a pyrrolidine ring, a piperidine ring, and an oxaline ring. Also, the so-called R 1' and the carbon atom at the 5th position of the dibenzopyran ring, R 3' and the carbon atom at the 7th position of the dibenzopyran ring, and R 2' and the carbon atom at the 4th position of the dibenzopyran ring. , or R 4' is bonded to the 2-position carbon atom of the dibenzopyran ring to form a ring structure, which means that R 1' to R 4' , and the above-mentioned carbon atoms at the specified position of the dibenzopyran ring. The combination forms a ring structure via a nitrogen atom and a part of the dibenzopyran skeleton, respectively. The ring structure is not particularly limited, and examples thereof include nitrogen-containing heterocycles having 5 to 7 members.

作為酸性基或其鹽之具體例,可列舉羧基(-COOH)、羧根基(-COO-)、羧酸鹽基(-COOM,此處M表示金屬原子)、磺酸基(-SO 3-)、磺基(-SO 3H)、磺酸鹽基(-SO 3M,此處M表示金屬原子)等,其中,較佳為具有磺酸基(-SO 3-)、磺基(-SO 3H)、或磺酸鹽基(-SO 3M)之至少一種。再者,作為金屬原子M,可列舉鈉原子、鉀原子等。 Specific examples of the acidic group or its salt include a carboxyl group (-COOH), a carboxyl group (-COO-), a carboxylate group (-COOM, where M represents a metal atom), a sulfonic acid group (-SO 3 - ), a sulfo group (-SO 3 H), a sulfonate group (-SO 3 M, where M represents a metal atom), etc., among which, it is preferable to have a sulfo group (-SO 3 -), a sulfo group (- At least one of SO 3 H), or sulfonate group (—SO 3 M). In addition, as the metal atom M, a sodium atom, a potassium atom, etc. are mentioned.

作為上述通式(5)所表示之二苯并哌喃系染料之具體例,可列舉:酸性紅50、酸性紅52、酸性紅289、酸性紫9、酸性紫30、酸性藍19等。Specific examples of the dibenzopyran-based dye represented by the general formula (5) include Acid Red 50, Acid Red 52, Acid Red 289, Acid Violet 9, Acid Violet 30, Acid Blue 19, and the like.

<色澱化劑> 二苯并哌喃系染料之金屬色澱色料之色澱化中所使用之色澱化劑只要為包含金屬原子之色澱化劑即可。作為包含金屬原子之色澱化劑,較佳為包含成為二價以上之金屬陽離子之金屬原子之色澱化劑,具體而言,可列舉氯化鋇、氯化鈣、碳酸鈣、氯化鋁、硫酸鋁、乙酸鋁、乙酸鉛、硫酸鎂、氯化鋯、硫酸鋯、碳酸鋯、聚氯化鋁、聚硫酸鋁等,其中,更佳為包含成為三價以上之金屬陽離子之金屬原子之色澱化劑。進而,就容易合成色澱色料、及色澱色料之分散性優異之觀點而言,較佳為包含鋁之色澱化劑。即,作為二苯并哌喃系染料之金屬色澱色料,較佳為二苯并哌喃系染料之鋁色澱色料,尤佳為上述通式(5)所表示之二苯并哌喃系染料之鋁色澱色料。 藉由使用包含成為三價陽離子之鋁之色澱化劑,而推定較包含成為二價金屬陽離子之金屬原子之色澱化劑,上述包含成為三價陽離子之鋁之色澱化劑作為色澱化劑其凝聚力更強。因此,經色澱化之二苯并哌喃系染料在溶劑中之溶解度大幅降低,成為更接近顏料之性質。因此,亦具有以下優點:色料之分散性及耐熱性優異,並且於製造色料時容易回收(過濾分離)色澱色料。 <Lakeizer> The lake-forming agent used for the lake-forming of the metallic lake color material of the dibenzopyran-based dye may be a lake-forming agent containing a metal atom. As a lake-forming agent containing a metal atom, a lake-forming agent containing a metal atom that becomes a metal cation with a divalent or higher value is preferable, and specific examples thereof include barium chloride, calcium chloride, calcium carbonate, and aluminum chloride. , aluminum sulfate, aluminum acetate, lead acetate, magnesium sulfate, zirconium chloride, zirconium sulfate, zirconium carbonate, polyaluminum chloride, polyaluminum sulfate, etc., among which, it is more preferable to contain a metal atom that becomes a metal cation of trivalent or more Lakers. Furthermore, from the viewpoint of easy synthesis of the lake color material and excellent dispersibility of the lake color material, a lake-forming agent containing aluminum is preferable. That is, as the metallic lake coloring material of the dibenzopyran-based dye, the aluminum lake coloring material of the dibenzopyran-based dye is preferable, and the dibenzophenone represented by the above-mentioned general formula (5) is particularly preferable. Aluminium lake colorant for pyran dyes. By using a lake-forming agent containing aluminum as a trivalent cation, it is estimated that the above-mentioned lake-forming agent containing aluminum as a trivalent cation is used as a lake rather than a lake-forming agent containing a metal atom as a divalent metal cation The chemical agent has stronger cohesion. Therefore, the solubility of the laked dibenzopyran-based dye in the solvent is greatly reduced, and the property is closer to that of a pigment. Therefore, it also has the following advantages: the dispersibility and heat resistance of the colorant are excellent, and the lake colorant is easily recovered (filtered and separated) when the colorant is produced.

作為包含鋁之色澱化劑,其中就色料之耐熱性優異之觀點、及容易抑制色料之昇華之觀點而言,較佳為下述通式(6)所表示之聚氯化鋁。Among them, polyaluminum chloride represented by the following general formula (6) is preferable from the viewpoint of excellent heat resistance of the colorant and the viewpoint of easily suppressing the sublimation of the colorant as the lake-forming agent containing aluminum.

[化12] 通式(6)

Figure 02_image027
(通式(6)中,n為2~20之整數,m為(n/2)~(3n-1)之整數) [Chemical 12] General formula (6)
Figure 02_image027
(In the general formula (6), n is an integer of 2 to 20, and m is an integer of (n/2) to (3n-1))

於上述通式(6)所表示之聚氯化鋁中,n表示鋁原子之數,為2~20個。藉由採用鋁原子為2~20個之相對較小之聚氯化鋁作為色澱化劑,色料之分散粒徑不會變得過大,可使色料之分散性變得良好。於本發明中,其中較佳為n為2~10之整數。In the polyaluminum chloride represented by the above general formula (6), n represents the number of aluminum atoms, and is 2 to 20. By using relatively small polyaluminum chloride with 2-20 aluminum atoms as the lake-forming agent, the dispersed particle size of the colorant will not become too large, and the dispersibility of the colorant can be improved. In this invention, it is preferable that n is an integer of 2-10 among them.

又,於上述通式(6)所表示之聚氯化鋁中,m表示羥基(OH -基)之數,為(n/2)~(3n-1)之整數。再者,於n為奇數之情形時,m之下限為在上述範圍內成為最小整數之{(n+1)/2}。 Moreover, in the polyaluminum chloride represented by the said general formula (6), m represents the number of a hydroxyl group ( OH- group), and is an integer of (n/2)-(3n-1). Furthermore, when n is an odd number, the lower limit of m is {(n+1)/2} which becomes the smallest integer within the above range.

聚氯化鋁中之鋁具有三價陽離子性,羥基具有一價陰離子性,因此整個聚氯化鋁具有(3n-m)價陽離子性。於本發明中,就凝聚力較強,容易回收色料,或者色料之分散性優異之觀點而言,其中較佳為鹼性較高,較佳為m為2n~(3n-1)之整數。 其中,就提高色料之分散性、及塗膜之對比度之觀點而言,上述通式(6)所表示之聚氯化鋁較佳為n為2~10之整數,且m為2n~(3n-1)之整數。 Aluminum in polyaluminum chloride has trivalent cation, and the hydroxyl group has monovalent anion, so the whole polyaluminum chloride has (3n-m) cation. In the present invention, from the viewpoint of strong cohesion, easy recovery of the colorant, or excellent dispersibility of the colorant, it is preferable that the basicity is high, and m is preferably an integer of 2n to (3n-1). . Among them, from the viewpoint of improving the dispersibility of the colorant and the contrast of the coating film, the polyaluminum chloride represented by the general formula (6) is preferably n is an integer of 2 to 10, and m is 2n to ( 3n-1) integer.

又,就色料之耐熱性進一步提高,容易抑制色料之昇華,且容易使色料之分散性變得良好之觀點而言,通式(6)所表示之聚氯化鋁較佳為由(m/3n×100(%))定義之鹼度為15~99%,更佳為60~97%,進而較佳為70~95%。In addition, the polyaluminum chloride represented by the general formula (6) is preferred from the viewpoints that the heat resistance of the colorant is further improved, the sublimation of the colorant is easily suppressed, and the dispersibility of the colorant is easily improved. The basicity defined by (m/3n×100(%)) is 15 to 99%, more preferably 60 to 97%, and further preferably 70 to 95%.

(C.I.顏料藍15:6) 本發明中被較佳地使用之C.I.顏料藍15:6係具有ε型結晶結構之酞菁銅顏料,就分散穩定性優異之觀點而言較佳。 對於本發明中所使用之C.I.顏料藍15:6,可進行鹼性處理或酸性處理,就分散性及保存穩定性優異之觀點而言,於組合使用之分散劑為酸性之情形時,較佳為進行鹼性處理;於組合使用之分散劑為鹼性之情形時,較佳為進行酸性處理。其中,本發明中所使用之C.I.顏料藍15:6較佳為被進行鹼性處理,經鹼性處理之C.I.顏料藍15:6較佳為與酸性分散劑組合而使用。 (C.I. Pigment Blue 15:6) The C.I. Pigment Blue 15:6 preferably used in the present invention is a copper phthalocyanine pigment having an ε-type crystal structure, and is preferred from the viewpoint of excellent dispersion stability. The C.I. Pigment Blue 15:6 used in the present invention can be subjected to an alkaline treatment or an acid treatment. From the viewpoint of excellent dispersibility and storage stability, it is preferable when the dispersant used in combination is acidic. In order to carry out alkaline treatment; when the dispersant used in combination is alkaline, acid treatment is preferably carried out. Among them, the C.I. Pigment Blue 15:6 used in the present invention is preferably alkali-treated, and the alkali-treated C.I. Pigment Blue 15:6 is preferably used in combination with an acidic dispersant.

於本發明中,鹼性處理時適宜使用具有鹼性部位之色料衍生物、或具有鹼性部位之無色化合物之衍生物。又,於本發明中,所謂具有鹼性部位,可列舉具有鹼性基作為取代基之態樣、於取代基處酸性基與鹼性化合物形成鹽之態樣等。 作為本發明中色料衍生物或無色化合物之衍生物所具有之鹼性部位,例如可列舉:胺基、磺酸銨鹽、或具有胺基之磺醯胺基、具有胺基之醯胺基、鹼性雜環基等。 In the present invention, a colorant derivative having an alkaline moiety or a derivative of a colorless compound having an alkaline moiety is suitably used in the alkaline treatment. Moreover, in this invention, what has a basic site includes the aspect which has a basic group as a substituent, the aspect which an acidic group and a basic compound form a salt at a substituent, etc. are mentioned. Examples of the basic moiety possessed by the colorant derivative or the colorless compound derivative in the present invention include an amine group, an ammonium sulfonate, a sulfonamido group having an amine group, and an amide group having an amine group. , basic heterocyclic groups, etc.

關於具有鹼性部位之色料衍生物中所使用之色料,可適宜選擇公知之色料來使用,較佳為具有容易與C.I.顏料藍15:6吸附之結構,較佳為具有相同或類似之色素骨架,或者具有容易進行交互作用之結構。又,較佳為不會對鹼性處理時所使用之C.I.顏料藍15:6之色調造成損害之色料。 作為具有鹼性部位之色料衍生物,其中較佳為藍色色料衍生物。作為具有鹼性部位之色料衍生物中所使用之藍色色料,可使用酞菁系色料、三芳基甲烷系色料、蒽醌系色料、萘酚系色料、苯并咪唑酮系色料等,單就色調或耐熱性之觀點而言,較佳為使用酞菁系色料。其中,就分散性及亮度提高之觀點而言,作為具有鹼性部位之色料衍生物中所使用之色料,較佳為使用下述酞菁系色料,該酞菁系色料具有與鹼性處理時所使用之C.I.顏料藍15:6相同之骨架。又,其中,就分散性及亮度提高之觀點而言,作為具有鹼性部位之色料衍生物中所使用之藍色色料,較佳為使用酞菁銅。 As for the colorant used in the colorant derivative having an alkaline moiety, a well-known colorant can be appropriately selected and used, preferably one having a structure that is easily adsorbed to C.I. Pigment Blue 15:6, preferably the same or similar The pigment skeleton, or has a structure that is easy to interact. Moreover, it is preferable that it does not damage the color tone of C.I. Pigment Blue 15:6 used in the alkaline treatment. Among the colorant derivatives having a basic moiety, blue colorant derivatives are preferred. As the blue colorant used in the colorant derivative having a basic moiety, phthalocyanine-based colorants, triarylmethane-based colorants, anthraquinone-based colorants, naphthol-based colorants, and benzimidazolone-based colorants can be used As for the colorant and the like, it is preferable to use a phthalocyanine-based colorant only from the viewpoint of color tone and heat resistance. Among them, from the viewpoint of improving dispersibility and brightness, as the colorant used in the colorant derivative having a basic moiety, it is preferable to use a phthalocyanine-based colorant having the same properties as The skeleton of C.I. Pigment Blue 15:6 used in the alkaline treatment is the same. Moreover, among these, it is preferable to use copper phthalocyanine as a blue coloring material used for the color material derivative|guide_body which has a basic part from a viewpoint of dispersibility and brightness improvement.

關於具有鹼性部位之無色化合物之衍生物中所使用之無色化合物,可將下述化合物作為標準,該化合物係即便使用該無色化合物之衍生物對C.I.顏料藍15:6進行鹼性處理,C.I.顏料藍15:6之顏色亦不會於鹼性處理前後發生變化。作為該無色化合物,例如可使用萘系、三𠯤系等縮合環化合物或鍵結有複數個芳香族環之芳香族多環化合物。作為三𠯤系芳香族多環化合物,例如可列舉在三𠯤環上,苯基胺基等具有芳香族烴基之取代基被取代了3個之結構。其中,就分散性及亮度提高之觀點而言,較佳為使用三𠯤系芳香族多環化合物。Regarding the leuco compound used in the derivative of the leuco compound having a basic moiety, the following compound can be used as a standard. Even if the derivative of the leuco compound is used for basic treatment of C.I. Pigment Blue 15:6, C.I. The color of Pigment Blue 15:6 will not change before and after alkaline treatment. As the colorless compound, for example, a condensed ring compound such as a naphthalene-based compound and a triazine-based compound, or an aromatic polycyclic compound in which a plurality of aromatic rings are bonded can be used. Examples of the trisic aromatic polycyclic compound include a structure in which three substituents having an aromatic hydrocarbon group, such as a phenylamino group, are substituted on the trisic ring. Among them, from the viewpoint of improving dispersibility and brightness, it is preferable to use a tris-based aromatic polycyclic compound.

關於例如製備包含具有鹼性部位之色料衍生物之C.I.顏料藍15:6作為具有源自鹼性化合物之結構之C.I.顏料藍15:6的方法,例如可列舉下述方法,即,將具有鹼性部位之色料衍生物、與C.I.顏料藍15:6進行乾式粉碎後,進而將具有鹼性部位之色料衍生物加以混合。於該情形時,作為乾式粉碎機,可使用球磨機、振磨機、磨碎機等,粉碎溫度可於20~130℃內自由設定。  又,作為製備包含具有鹼性部位之色料衍生物之C.I.顏料藍15:6之方法,可列舉如下方法等:將具有鹼性部位之色料衍生物、C.I.顏料藍15:6、及氯化鈉、氯化鈣、硫酸銨等水溶性無機鹽、以及二醇系有機溶劑等水溶性有機溶劑加以混合,藉由溶劑鹽磨法並利用捏合機型研磨機進行混練。 於色料分散前預先製備或準備經鹼性處理之C.I.顏料藍15:6,使色料分散,藉此可提高色料分散性。 As a method of preparing, for example, C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety as C.I. Pigment Blue 15:6 having a structure derived from a basic compound, for example, a method of After dry grinding the color derivative with basic part and C.I. Pigment Blue 15:6, the color derivative with basic part is mixed. In this case, as a dry pulverizer, a ball mill, a vibration mill, an attritor, etc. can be used, and the pulverization temperature can be freely set within 20 to 130°C. In addition, as a method for preparing C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety, there may be mentioned a method in which a colorant derivative having a basic moiety, C.I. Pigment Blue 15:6, and chlorine Water-soluble inorganic salts such as sodium chloride, calcium chloride, and ammonium sulfate, and water-soluble organic solvents such as glycol-based organic solvents are mixed, and kneaded by a solvent-salt milling method using a kneader-type mill. Before dispersing the colorant, prepare or prepare the alkaline treated C.I. Pigment Blue 15:6 to disperse the colorant, thereby improving the dispersibility of the colorant.

於包含具有鹼性部位之色料衍生物或無色化合物之衍生物的C.I.顏料藍15:6中,就分散性及保存穩定性之觀點而言,具有鹼性部位之色料衍生物或無色化合物之衍生物之含量相對於C.I.顏料藍15:6 100質量份,較佳為0.5質量份以上,更佳為3質量份以上,進而較佳為5質量份以上,進而更佳為8質量份以上。另一方面,就亮度優異之觀點而言,具有鹼性部位之色料衍生物或無色化合物之衍生物之含量相對於C.I.顏料藍15:6 100質量份,較佳為50質量份以下,更佳為40質量份以下,進而較佳為30質量份以下。In C.I. Pigment Blue 15:6 containing a colorant derivative having a basic moiety or a colorless compound derivative, from the viewpoint of dispersibility and storage stability, a colorant derivative having a basic moiety or a colorless compound The content of the derivative of C.I. Pigment Blue 15:6 100 parts by mass is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and still more preferably 8 parts by mass or more . On the other hand, from the viewpoint of being excellent in brightness, the content of the colorant derivative having a basic moiety or the derivative of the leuco compound is 100 parts by mass relative to C.I. Pigment Blue 15:6, preferably 50 parts by mass or less, and more Preferably it is 40 mass parts or less, More preferably, it is 30 mass parts or less.

再者,關於經鹼性處理或酸性處理之C.I.顏料藍15:6,例如可使用質量分析、元素分析、表面分析、電位滴定、及其等之組合來適當地分析。 又,作為與經鹼性處理之C.I.顏料藍15:6組合而使用之酸性分散劑,可列舉可用於下述色料分散液之酸性分散劑相同者。 Furthermore, with respect to C.I. Pigment Blue 15:6 treated with an alkaline treatment or an acid treatment, for example, mass analysis, elemental analysis, surface analysis, potentiometric titration, and a combination thereof can be used for analysis as appropriate. Moreover, as an acidic dispersing agent used in combination with the alkaline-treated C.I. Pigment Blue 15:6, the same acidic dispersing agent which can be used for the following color material dispersion liquid can be mentioned.

於本發明中,就著色層之亮度容易提高之觀點而言,相對於色料之總量100質量份,染料及色澱色料之合計含量較佳為5質量份以上100質量份以下,更佳為10質量份以上100質量份以下。 其中,就可獲得高亮度之著色層之觀點、及色料與含有(甲基)丙烯酸羥烷基酯單元之共聚物之相容性提高使得抑制顯影殘渣之效果提高之觀點而言,相對於色料之總量100質量份,色澱色料之含量較佳為20質量份以上100質量份以下,更佳為30質量份以上100質量份以下。 進而就可獲得高亮度之著色層之觀點而言,相對於色料之總量100質量份,上述通式(1)或通式(2)所表示之色澱色料之合計含量較佳為20質量份以上100質量份以下,更佳為30質量份以上100質量份以下。若上述通式(1)或通式(2)所表示之色澱色料之合計含量為上述下限值以上,則就色料與含有(甲基)丙烯酸羥烷基酯單元之共聚物之相容性提高使得抑制顯影殘渣之效果提高之觀點、及耐熱性提高之觀點而言亦較佳。 於色料包含上述通式(1)或通式(2)所表示之色澱色料、及與該色澱色料不同之色料之組合之情形時,以可獲得所需色調之方式進行調色,雖無特別限定,但就可獲得高亮度之著色層之觀點、色料與含有(甲基)丙烯酸羥烷基酯單元之共聚物之相容性提高使得抑制顯影殘渣之效果提高之觀點、及耐熱性提高之觀點而言,相對於色料之總量100質量份,上述通式(1)或通式(2)所表示之色澱色料之合計含量較佳為20質量份以上98質量份以下,亦可為30質量份以上95質量份以下。 於色料包含上述通式(1)或通式(2)所表示之色澱色料、以及選自由二苯并哌喃系染料、及與上述通式(1)或通式(2)所表示之色澱色料不同之二苯并哌喃系染料之色澱色料所組成之群中之至少一種之情形時,就獲得所需色相之觀點而言,相對於色料之總量100質量份,該二苯并哌喃系染料及該二苯并哌喃系染料之色澱色料之合計含量可為2質量份以上,亦可為5質量份以上,另一方面,就抑制耐熱性降低之觀點而言,較佳為30質量份以下,亦可為25質量份以下。 又,於色料包含上述通式(1)或通式(2)所表示之色澱色料、及C.I.顏料藍15:6之情形時,就獲得所需色相之觀點而言,相對於色料之總量100質量份,C.I.顏料藍15:6之含量可為20質量份以上,亦可為30質量份以上,另一方面,就抑制著色層之亮度降低之觀點、及抑制顯影殘渣產生且抑制色料之耐熱性降低之觀點而言,較佳為80質量份以下,亦可為70質量份以下。 In the present invention, from the viewpoint of easily improving the brightness of the colored layer, the total content of dyes and lake colorants is preferably 5 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the total amount of colorants. It is preferably 10 parts by mass or more and 100 parts by mass or less. Among them, from the viewpoint of obtaining a high-brightness colored layer, and from the viewpoint that the compatibility of the colorant with the copolymer containing hydroxyalkyl (meth)acrylate units is improved, and the effect of suppressing the development residue is improved, compared with the viewpoint of The total amount of the colorant is 100 parts by mass, and the content of the lake colorant is preferably 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less. Furthermore, from the viewpoint of obtaining a high-brightness coloring layer, the total content of the lake colorant represented by the general formula (1) or the general formula (2) is preferably 100 parts by mass of the total amount of the colorant. 20 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 100 parts by mass or less. If the total content of the lake colorant represented by the general formula (1) or the general formula (2) is more than the above lower limit value, the total content of the colorant and the copolymer containing hydroxyalkyl (meth)acrylate units Compatibility improvement is also preferable from the viewpoint of improving the effect of suppressing development residue, and the viewpoint of improving heat resistance. In the case where the colorant contains the lake colorant represented by the above general formula (1) or the general formula (2), and the combination of the colorant different from the lake colorant, it is carried out in such a way that the desired hue can be obtained. Toning, although not particularly limited, can be obtained from the viewpoint of obtaining a high-brightness colored layer, the compatibility of the colorant with the copolymer containing hydroxyalkyl (meth)acrylate units is improved, and the effect of suppressing development residues is improved. From the viewpoint and the viewpoint of improving heat resistance, the total content of the lake colorant represented by the general formula (1) or the general formula (2) is preferably 20 parts by mass relative to 100 parts by mass of the total amount of the colorant. More than 98 mass parts or less, and 30 mass parts or more and 95 mass parts or less may be sufficient. The colorant includes a lake coloring material represented by the above general formula (1) or general formula (2), and a dye selected from the group consisting of dibenzopyran series and the above general formula (1) or general formula (2). In the case of at least one of the group consisting of the lake colorants of dibenzopyran-based dyes with different lake colorants, from the viewpoint of obtaining the desired hue, relative to the total amount of colorants 100 Parts by mass, the total content of the dibenzopyran-based dye and the lake colorant of the dibenzopyran-based dye may be 2 parts by mass or more, and may also be more than 5 parts by mass. From the viewpoint of lowering the properties, it is preferably 30 parts by mass or less, and may be 25 parts by mass or less. In addition, when the colorant contains the lake colorant represented by the general formula (1) or the general formula (2), and C.I. Pigment Blue 15:6, from the viewpoint of obtaining the desired hue, relative to the color The total amount of materials is 100 parts by mass, and the content of C.I. Pigment Blue 15:6 may be 20 parts by mass or more, and may be 30 parts by mass or more. On the other hand, from the viewpoint of suppressing the decrease in brightness of the colored layer and suppressing the generation of development residues And from a viewpoint of suppressing the fall of the heat resistance of a coloring material, 80 mass parts or less are preferable, and 70 mass parts or less may be sufficient.

又,相對於本發明之感光性著色樹脂組合物之固形物成分總量,染料及色澱色料之含量通常為0.5質量%以上35質量%以下,較佳為1質量%以上30質量%以下,更佳為2質量%以上25質量%以下。Moreover, the content of the dye and the lake coloring material is usually 0.5 mass % or more and 35 mass % or less, preferably 1 mass % or more and 30 mass % or less with respect to the total solid content of the photosensitive colored resin composition of the present invention. , more preferably 2 mass % or more and 25 mass % or less.

<其他顏料> 本發明之感光性著色樹脂組合物可在無損本發明之效果之範圍內進而包含與上述C.I.顏料藍15:6不同之其他顏料,以調整色調。作為該其他顏料,可使用先前作為彩色濾光片之著色劑而使用之各種有機顏料及無機顏料,並無特別限定,單就顯色性及耐熱性優異之觀點而言,較佳為有機顏料。 <Other pigments> The photosensitive colored resin composition of the present invention may further contain other pigments different from the above-mentioned C.I. Pigment Blue 15:6 within a range that does not impair the effects of the present invention to adjust the color tone. As the other pigments, various organic pigments and inorganic pigments that have been used as colorants for color filters can be used, and are not particularly limited, but organic pigments are preferred from the viewpoint of being excellent in color rendering properties and heat resistance. .

於藍色用途之情形時,作為上述其他顏料,就分散穩定性優異之觀點而言,可較佳地使用具有ε型或β型結晶結構之酞菁銅顏料等藍色顏料、以及C.I.顏料紫23等紫色顏料。作為具有ε型或β型結晶結構之酞菁銅顏料,其中,可較佳地使用選自由C.I.顏料藍15、15:1、15:2、15:3、15:4及15:5所組成之群中之至少一種。 再者,上述其他顏料可與C.I.顏料藍15:6同樣地經酸性處理或鹼性處理,以提高分散穩定性。關於上述其他顏料,同樣地於組合使用之分散劑為酸性之情形時,較佳為經鹼性處理,於組合使用之分散劑為鹼性之情形時,較佳為經酸性處理。 In the case of blue applications, as the other pigments mentioned above, blue pigments such as copper phthalocyanine pigments having an ε-type or β-type crystal structure, and C.I. Pigment Violet can be preferably used from the viewpoint of excellent dispersion stability. 23 and other purple pigments. As a copper phthalocyanine pigment having an ε-type or β-type crystal structure, among them, the group consisting of C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 and 15:5 can be preferably used at least one of the group. In addition, the above-mentioned other pigments can be acid-treated or alkaline-treated similarly to C.I. Pigment Blue 15:6 to improve dispersion stability. As for the other pigments mentioned above, similarly, when the dispersant used in combination is acidic, it is preferably subjected to alkaline treatment, and when the dispersant used in combination is alkaline, it is preferably subjected to acidic treatment.

於本發明中,上述其他顏料較佳為以無損本發明之效果之範圍內之量進行使用。具體而言,較佳為相對於感光性著色樹脂組合物之固形物成分總量,將上述其他顏料之含量設為25質量%以下,或者相對於染料及色澱色料之總量100質量份,將上述其他顏料之含量設為80質量份以下。進而,將上述2個上限量中之較少量作為更佳之上限量。In the present invention, the other pigments described above are preferably used in an amount within a range that does not impair the effects of the present invention. Specifically, the content of the other pigments is preferably 25% by mass or less relative to the total solid content of the photosensitive colored resin composition, or 100 parts by mass relative to the total amount of dyes and lake colorants , the content of the above-mentioned other pigments is set to 80 parts by mass or less. Furthermore, the smaller of the above-mentioned two upper limit amounts is set as a more preferable upper limit amount.

[黏合劑樹脂] <含有(甲基)丙烯酸羥烷基酯單元之共聚物> 本發明之感光性著色樹脂組合物所含有之黏合劑樹脂包含下述共聚物(含有(甲基)丙烯酸羥烷基酯單元之共聚物),該共聚物具有包含5~25質量%之下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元的高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g。 上述含有(甲基)丙烯酸羥烷基酯單元之共聚物係於高分子骨架之鏈結構內包含源自(甲基)丙烯酸羥烷基酯之結構單元之鹼可溶性共聚物。 含有(甲基)丙烯酸羥烷基酯單元之共聚物所具有之高分子結構可為僅具有主鏈之結構,亦可為具有主鏈與側鏈之結構。含有(甲基)丙烯酸羥烷基酯單元之共聚物之主鏈,典型而言具有藉由具有乙烯性不飽和鍵之單體之加成聚合而產生之結構單元進行連結而成之鏈結構,進而可包含藉由具有乙烯性不飽和鍵以外之官能基之單體之加成聚合或縮聚合而產生之結構單元。 含有(甲基)丙烯酸羥烷基酯單元之共聚物之側鏈,典型而言經由藉由主鏈上之官能基與用以形成側鏈之單體之官能基的反應而產生之連結基而鍵結於主鏈,亦可經由碳-碳間之鍵而自主鏈分支出去。 作為主鏈上之官能基與用以形成側鏈之單體之官能基進行反應而形成側鏈之例,例如於主鏈上存在羧基之情形時,藉由使具有縮水甘油基之單體與該羧基反應而形成酯連結基,可導入下述側鏈,該側鏈包含源自具有縮水甘油基之單體之結構單元。又,作為其他例,於主鏈上存在羥基之情形時,藉由使具有異氰酸基之單體與該羥基反應而形成胺基甲酸酯連結基,可導入下述側鏈,該側鏈包含源自具有異氰酸基之單體之結構單元。 側鏈可為具有1個單體之結構單元之側鏈結構(pendant structure),亦可具有由2個以上結構單元連結而成之聚合物結構。又,於側鏈具有聚合物結構之情形時,可僅由源自具有乙烯性不飽和鍵之單體之結構單元所構成,亦可包含藉由具有乙烯性不飽和鍵以外之官能基之單體之加成聚合或縮聚合而產生之結構單元。 含有(甲基)丙烯酸羥烷基酯單元之共聚物除具有源自(甲基)丙烯酸羥烷基酯之羥基以外,還視需要具有能賦予鹼可溶性之酸性基、含乙烯性雙鍵之基之類之其他官能基、大體積基(bulky group)之類之調節分子結構之基等原子團,其等可存在於主鏈或側鏈之任一處。 [binder resin] <Copolymer containing hydroxyalkyl (meth)acrylate units> The binder resin contained in the photosensitive colored resin composition of the present invention contains the following copolymer (copolymer containing a hydroxyalkyl (meth)acrylate unit) containing 5 to 25% by mass of the following The polymer structure of the structural unit derived from the hydroxyalkyl (meth)acrylate represented by the general formula (A) has a weight average molecular weight of 11,000 or more and an acid value of 60 to 130 mgKOH/g. The above-mentioned copolymer containing a hydroxyalkyl (meth)acrylate unit is an alkali-soluble copolymer containing a structural unit derived from a hydroxyalkyl (meth)acrylate in the chain structure of the polymer backbone. The polymer structure of the copolymer containing a hydroxyalkyl (meth)acrylate unit may be a structure having only a main chain or a structure having a main chain and a side chain. The main chain of the copolymer containing a hydroxyalkyl (meth)acrylate unit typically has a chain structure formed by linking structural units produced by addition polymerization of a monomer having an ethylenically unsaturated bond, Furthermore, the structural unit produced by addition polymerization or polycondensation polymerization of the monomer which has a functional group other than an ethylenically unsaturated bond can be contained. The side chains of copolymers containing hydroxyalkyl (meth)acrylate units are typically formed by linking groups generated by the reaction of functional groups on the main chain with functional groups of the monomers used to form the side chains. It is bonded to the main chain, and can also be branched from the main chain through carbon-carbon bonds. As an example of forming a side chain by reacting a functional group on the main chain with a functional group of a monomer for forming a side chain, for example, when a carboxyl group exists on the main chain, the monomer having a glycidyl group is reacted with The carboxyl group reacts to form an ester linking group, and a side chain including a structural unit derived from a monomer having a glycidyl group can be introduced. As another example, when a hydroxyl group exists in the main chain, the following side chain can be introduced by reacting a monomer having an isocyanate group with the hydroxyl group to form a urethane linking group. The chain contains structural units derived from monomers having isocyanate groups. The side chain may have a pendant structure having a structural unit of one monomer, or may have a polymer structure formed by linking two or more structural units. In addition, when the side chain has a polymer structure, it may be composed of only a structural unit derived from a monomer having an ethylenically unsaturated bond, or may include a single unit derived from a functional group other than an ethylenically unsaturated bond. Structural units produced by addition or condensation polymerization. The copolymer containing a hydroxyalkyl (meth)acrylate unit has, in addition to a hydroxyl group derived from a hydroxyalkyl (meth)acrylate, an acidic group capable of imparting alkali solubility and a group containing an ethylenic double bond as necessary Atomic groups such as other functional groups such as bulky groups, groups that adjust molecular structure such as bulky groups, etc., can be present in either the main chain or the side chain.

作為含有(甲基)丙烯酸羥烷基酯單元之共聚物之較佳之一例,可列舉下述側鏈與下述主鏈鍵結而成之共聚物,上述側鏈包含具有乙烯性不飽和鍵等光聚合性官能基之結構單元,上述主鏈包含源自(甲基)丙烯酸羥烷基酯之結構單元、具有酸性基之結構單元、具有大體積基之結構單元、及視需要而定之其他結構單元。 此種含有(甲基)丙烯酸羥烷基酯單元之共聚物藉由主鏈上之酸性基而被賦予鹼可溶性,藉由側鏈之光聚合性官能基而被賦予了交聯鍵結性。於含有(甲基)丙烯酸羥烷基酯單元之共聚物具有光聚合性官能基之情形時,在製造彩色濾光片時之樹脂組合物之硬化步驟中,黏合劑樹脂彼此、或黏合劑樹脂與作為光聚合性化合物之單體等能夠形成交聯鍵。其結果為,硬化膜之膜強度進一步提高,耐顯影性提高,又,硬化膜之熱縮得到抑制,與基板之密接性變得優異。 A preferable example of a copolymer containing a hydroxyalkyl (meth)acrylate unit includes a copolymer in which the following side chain is bonded to the following main chain, and the side chain includes an ethylenically unsaturated bond, etc. A structural unit of a photopolymerizable functional group, the main chain includes a structural unit derived from hydroxyalkyl (meth)acrylate, a structural unit with an acidic group, a structural unit with a bulky group, and other structures as required unit. The copolymer containing such a hydroxyalkyl (meth)acrylate unit is provided with alkali solubility by the acidic group on the main chain, and is provided with crosslinking bondability by the photopolymerizable functional group in the side chain. When the copolymer containing a hydroxyalkyl (meth)acrylate unit has a photopolymerizable functional group, in the curing step of the resin composition in the production of a color filter, the binder resins or the binder resins A crosslinking bond can be formed with a monomer or the like which is a photopolymerizable compound. As a result, the film strength of the cured film is further improved, the development resistance is improved, and the thermal shrinkage of the cured film is suppressed, and the adhesiveness with the substrate becomes excellent.

作為上述較佳之含有(甲基)丙烯酸羥烷基酯單元之共聚物,例如可藉由以下方式而製造導入有具有光聚合性官能基之側鏈之含有(甲基)丙烯酸羥烷基酯單元之共聚物:使具有碳數1~4之伸烷基之(甲基)丙烯酸羥烷基酯、具有酸性基之乙烯性不飽和單體、具有大體積基之乙烯性不飽和單體、及視需要而定之其他乙烯性不飽和單體進行共聚,藉此合成主鏈部分,然後使具有與主鏈上之官能基反應而產生鍵之官能基、及光聚合性官能基之含光聚合性官能基之單體與其反應。 以下,對構成含有(甲基)丙烯酸羥烷基酯單元之共聚物之主鏈及側鏈之結構單元、及用於形成該結構單元之單體進行說明。 As the above-mentioned preferred hydroxyalkyl (meth)acrylate unit-containing copolymer, a hydroxyalkyl (meth)acrylate unit-containing copolymer into which a side chain having a photopolymerizable functional group is introduced can be produced, for example, as follows Copolymers: hydroxyalkyl (meth)acrylates with alkylene groups having 1 to 4 carbon atoms, ethylenically unsaturated monomers with acidic groups, ethylenically unsaturated monomers with bulky groups, and Other ethylenically unsaturated monomers as needed are copolymerized to synthesize the main chain part, and then the photopolymerizable functional group with a functional group that reacts with the functional group on the main chain to generate a bond and a photopolymerizable functional group The monomer of the functional group reacts with it. Hereinafter, the structural unit which comprises the main chain and the side chain of the copolymer containing a hydroxyalkyl (meth)acrylate unit, and the monomer for forming this structural unit are demonstrated.

(通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元) 下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元(以下,有時稱為「(甲基)丙烯酸羥烷基酯單元」)具有下述化學結構,該化學結構係具有碳數1~4之伸烷基之(甲基)丙烯酸羥烷基酯之乙烯性雙鍵因加成反應而斷鍵,產生了2個單鍵。 (Structural unit derived from hydroxyalkyl (meth)acrylate represented by general formula (A)) The structural unit derived from hydroxyalkyl (meth)acrylate (hereinafter, sometimes referred to as "hydroxyalkyl (meth)acrylate unit") represented by the following general formula (A) has the following chemical structure, The chemical structure is that the ethylenic double bond of the hydroxyalkyl (meth)acrylate having an alkylene group having 1 to 4 carbon atoms is cleaved due to an addition reaction, resulting in two single bonds.

[化13] 通式(A)

Figure 02_image029
(通式(A)中,R A表示甲基或氫原子,R B表示碳數1~4之伸烷基) [Chem. 13] General formula (A)
Figure 02_image029
(In the general formula (A), R A represents a methyl group or a hydrogen atom, and R B represents an alkylene group having 1 to 4 carbon atoms)

作為上述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元,其中較佳為上述通式(A)中之R A為甲基之源自甲基丙烯酸羥烷基酯之結構單元。 作為上述通式(A)所表示之(甲基)丙烯酸羥烷基酯單元之具體例,例如可列舉源自(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基-1-甲基乙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基異丁酯等(甲基)丙烯酸羥烷基酯之結構單元等。其中,較佳為源自(甲基)丙烯酸2-羥基乙酯之結構單元、源自(甲基)丙烯酸2-羥基丙酯之結構單元及源自(甲基)丙烯酸2-羥基-1-甲基乙酯之結構單元,尤佳為源自(甲基)丙烯酸2-羥基乙酯之結構單元。 As the structural unit derived from hydroxyalkyl (meth)acrylate represented by the above-mentioned general formula (A), it is preferable that R A in the above-mentioned general formula (A) is a methyl group derived from hydroxyalkane methacrylate The structural unit of the base ester. Specific examples of the hydroxyalkyl (meth)acrylate unit represented by the general formula (A) include those derived from hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( 2-hydroxypropyl meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxyisobutyl (meth)acrylate, etc. ( Structural unit of hydroxyalkyl meth)acrylate, etc. Among them, the structural unit derived from 2-hydroxyethyl (meth)acrylate, the structural unit derived from 2-hydroxypropyl (meth)acrylate, and the structural unit derived from 2-hydroxy-1-(meth)acrylate are preferred. The structural unit of methyl ethyl ester is particularly preferably a structural unit derived from 2-hydroxyethyl (meth)acrylate.

於本發明中,相對於構成共聚物之結構單元之總量100質量%,將含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之(甲基)丙烯酸羥烷基酯單元之量設為5質量%以上25質量%以下。藉由使(甲基)丙烯酸羥烷基酯單元之量處於上述範圍內,可獲得平坦性優異且顯影殘渣得到抑制之著色層。 於(甲基)丙烯酸羥烷基酯單元之量未達5質量%之情形時,在對感光性著色樹脂組合物之塗膜進行加熱乾燥時,無法充分地抑制塗膜之流動化,因此所獲得之著色層之平坦性變差。另一方面,於(甲基)丙烯酸羥烷基酯單元之量超過25質量%之情形時,會因感光性著色樹脂組合物之黏度上升而導致塗佈性變差或感光性著色樹脂組合物之溶劑再溶解性降低,由此所獲得之著色層容易產生異物或不均。 其中,含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之(甲基)丙烯酸羥烷基酯單元之量較佳為5質量%以上20質量%以下。 In the present invention, with respect to 100% by mass of the total amount of the structural units constituting the copolymer, the percentage of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing the hydroxyalkyl (meth)acrylate unit The amount is 5 mass % or more and 25 mass % or less. By making the quantity of a hydroxyalkyl (meth)acrylate unit into the said range, the coloring layer which is excellent in flatness and the development residue is suppressed can be obtained. When the amount of the hydroxyalkyl (meth)acrylate unit is less than 5% by mass, when the coating film of the photosensitive coloring resin composition is heated and dried, the fluidization of the coating film cannot be sufficiently suppressed, so the The flatness of the obtained coloring layer was deteriorated. On the other hand, when the amount of the hydroxyalkyl (meth)acrylate unit exceeds 25% by mass, the viscosity of the photosensitive colored resin composition may increase, resulting in poor coating properties or the photosensitive colored resin composition. The solvent re-solubility decreases, and foreign matter or unevenness is easily generated in the coloring layer obtained thereby. Among these, it is preferable that the quantity of the hydroxyalkyl (meth)acrylate unit contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is 5 mass % or more and 20 mass % or less.

(具有酸性基之結構單元) 於具有酸性基之結構單元中,作為酸性基,例如可列舉羧基、磷酸基、磺基等,其中就容易導入具有光聚合性官能基之側鏈之觀點而言,較佳為羧基。作為具有酸性基之結構單元,例如可較佳地使用源自具有羧基之乙烯性不飽和單體之結構單元。源自具有羧基之乙烯性不飽和單體之結構單元具有下述化學結構,該化學結構係具有羧基之乙烯性不飽和單體之乙烯性不飽和鍵因加成反應而斷鍵,產生了2個單鍵。 再者,於本發明中,源自乙烯性不飽和單體之結構單元意指乙烯性不飽和單體之可自由基聚合之碳-碳雙鍵變成了碳-碳單鍵之結構單元。 作為具有羧基之乙烯性不飽和單體,例如可列舉:(甲基)丙烯酸、乙烯基苯甲酸、順丁烯二酸、順丁烯二酸單烷基酯、反丁烯二酸、伊康酸、丁烯酸、肉桂酸、丙烯酸二聚物等。又,亦可使用(甲基)丙烯酸2-羥基乙酯或(甲基)丙烯酸4-羥基丁酯等具有羥基之單體、與順丁烯二酸酐、琥珀酸酐、鄰苯二甲酸酐、環己烷二羧酸酐之類之環狀酸酐之加成反應物、ω-羧基-聚己內酯單(甲基)丙烯酸酯等。又,亦可使用順丁烯二酸酐、伊康酸酐、檸康酸酐等含酸酐單體作為羧基之前驅物。其中,就共聚性及成本、溶解性、玻璃轉移溫度等觀點而言,尤佳為(甲基)丙烯酸。 (Structural unit with acidic group) In the structural unit which has an acidic group, as an acidic group, a carboxyl group, a phosphoric acid group, a sulfo group etc. are mentioned, for example, Among them, a carboxyl group is preferable from a viewpoint of easy introduction of the side chain which has a photopolymerizable functional group. As the structural unit having an acidic group, for example, a structural unit derived from an ethylenically unsaturated monomer having a carboxyl group can be preferably used. The structural unit derived from an ethylenically unsaturated monomer having a carboxyl group has the following chemical structure, which is that the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a carboxyl group is broken due to an addition reaction, resulting in 2 a single key. Furthermore, in the present invention, a structural unit derived from an ethylenically unsaturated monomer means a structural unit in which a radically polymerizable carbon-carbon double bond of the ethylenically unsaturated monomer becomes a carbon-carbon single bond. Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth)acrylic acid, vinylbenzoic acid, maleic acid, monoalkyl maleic acid, fumaric acid, Icon acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, monomers having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, together with maleic anhydride, succinic anhydride, phthalic anhydride, cyclic Addition reaction products of cyclic acid anhydrides such as hexanedicarboxylic anhydride, ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. In addition, acid anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and glass transition temperature.

關於含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之具有酸性基之結構單元之量,相對於構成共聚物之結構單元之總量100質量%,較佳為8質量%以上30質量%以下。藉由使具有酸性基之結構單元之量處於上述範圍內,可對感光性著色樹脂組合物之塗膜賦予充分之鹼可溶性,且可抑制溶劑溶解性之降低。 於具有酸性基之結構單元之量未達8質量%之情形時,酸值過低,而可能無法獲得充分之鹼可溶性。另一方面,於具有酸性基之結構單元之量超過30質量%之情形時,感光性樹脂組合物之極性過高,而可能難以溶解於溶劑中。 具有酸性基之結構單元之量更佳為10質量%以上28質量%以下,進而較佳為12質量%以上28質量%以下。 The amount of the structural unit having an acidic group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 8% by mass or more with respect to 100% by mass of the total amount of the structural units constituting the copolymer 30 mass % or less. By making the quantity of the structural unit which has an acidic group in the said range, sufficient alkali solubility can be provided to the coating film of the photosensitive coloring resin composition, and the fall of solvent solubility can be suppressed. When the amount of the structural unit having an acidic group is less than 8% by mass, the acid value is too low, and sufficient alkali solubility may not be obtained. On the other hand, when the quantity of the structural unit which has an acidic group exceeds 30 mass %, the polarity of the photosensitive resin composition is too high, and it may become difficult to melt|dissolve in a solvent. The amount of the structural unit having an acidic group is more preferably 10 mass % or more and 28 mass % or less, and still more preferably 12 mass % or more and 28 mass % or less.

(具有大體積基之結構單元) 作為具有大體積基之結構單元,例如可列舉源自具有大體積基之乙烯性不飽和單體之結構單元。源自具有大體積基之乙烯性不飽和單體之結構單元具有下述化學結構,該化學結構係具有大體積基之乙烯性不飽和單體之乙烯性不飽和鍵因加成反應而斷鍵,產生了2個單鍵。 於含有(甲基)丙烯酸羥烷基酯單元之共聚物具有大體積基之情形時,在黏合劑樹脂之硬化時收縮得到抑制,與基板間之剝離得到緩和,而提高對基板之密接性。再者,大體積基可以一價基之形式包含,亦可以二價以上之基之形式包含。 作為此種大體積基,例如可列舉:可具有取代基之脂肪族烴環、可具有取代基之芳香族烴環、及其等之組合等烴環。該烴環可具有烷基、環烷基、烷基環烷基、羰基、羧基、氧羰基、醯胺基、羥基、硝基、胺基、鹵素原子等取代基。 作為烴環之具體例,可列舉: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、二苯甲烷、三苯甲烷、茋等鏈狀多環、或Cardo結構(9,9-二芳基茀);該等基之一部分被取代基取代所得之基等。 於包含脂肪族烴環作為烴環之情形時,著色層之耐熱性及密接性提高,並且所獲得之著色層之亮度提高,就該方面而言較佳。 又,於結構單元包含上述Cardo結構之情形時,著色層之硬化性提高,可抑制色料之褪色,耐溶劑性(抑制NMP(N-Methyl pyrrolidone,N-甲基吡咯啶酮)膨潤)提高,就該方面而言尤佳。 (structural unit with bulky base) As a structural unit which has a bulky group, the structural unit derived from the ethylenically unsaturated monomer which has a bulky group is mentioned, for example. The structural unit derived from an ethylenically unsaturated monomer having a bulky group has the following chemical structure, and the chemical structure is that the ethylenically unsaturated bond of the ethylenically unsaturated monomer having a bulky group is broken by addition reaction. , resulting in 2 single bonds. When the copolymer containing a hydroxyalkyl (meth)acrylate unit has a bulky group, shrinkage during curing of the adhesive resin is suppressed, peeling from the substrate is alleviated, and adhesion to the substrate is improved. In addition, the bulky group may be contained in the form of a monovalent group, or may be contained in the form of a bivalent or higher group. Examples of such bulky groups include hydrocarbon rings such as an aliphatic hydrocarbon ring which may have a substituent, an aromatic hydrocarbon ring which may have a substituent, and combinations thereof. The hydrocarbon ring may have substituents such as an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, a hydroxyl group, a nitro group, an amino group, a halogen atom, and the like. Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, noroxane, isoxane, tricyclo[5.2.1.0(2,6)]decane (bicyclo aliphatic hydrocarbon rings such as pentane) and adamantane; aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and stilbene; chain polycyclic rings such as biphenyl, triphenyl, diphenylmethane, triphenylmethane, and stilbene, or Cardo structure (9,9-diaryl fluoride); a group obtained by substituting a part of these groups with a substituent, etc. In the case where an aliphatic hydrocarbon ring is included as the hydrocarbon ring, the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the structural unit includes the above-mentioned Cardo structure, the curability of the colored layer is improved, the discoloration of the colorant can be suppressed, and the solvent resistance (swelling of NMP (N-Methyl pyrrolidone, N-methyl pyrrolidone) is suppressed) is improved. , which is particularly good in this regard.

作為具有烴環之乙烯性不飽和單體,例如可列舉:(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不變之效果較大之觀點而言,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)丙烯酸金剛烷酯、(甲基)丙烯酸苄酯、及苯乙烯中之至少一種。Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, and iso(meth)acrylate Base ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., from the viewpoint that the cross-sectional shape of the coloring layer after development is also maintained unchanged during heat treatment. In other words, it is preferable to use at least one selected from cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, and styrene .

關於含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之具有大體積基之結構單元之量,相對於構成共聚物之結構單元之總量100質量%,較佳為20質量%以上70質量%以下。藉由使具有大體積基之結構單元之量處於該範圍內,可使塗膜對基板之密接性變得優異。 於具有大體積基之結構單元之量未達20質量%之情形時,可能導致塗膜對基板之密接性變得不充分。另一方面,於具有大體積基之結構單元之量超過70質量%之情形時,可能無法充分地導入(甲基)丙烯酸羥烷基酯單元、酸性基或光聚合性官能基,導致感光性著色樹脂組合物之顯影性或造膜形成性、或者所獲得之著色層之平坦性變得不充分。 具有大體積基之結構單元之量更佳為20質量%以上60質量%以下,進而較佳為20質量%以上55質量%以下。 The amount of the structural unit having a bulky group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 20% by mass with respect to 100% by mass of the total amount of the structural units constituting the copolymer More than 70 mass % or less. By making the quantity of the structural unit which has a bulky group within this range, the adhesiveness of a coating film with respect to a board|substrate becomes excellent. When the amount of the structural unit having a bulky base is less than 20% by mass, the adhesiveness of the coating film to the substrate may become insufficient. On the other hand, in the case where the amount of the structural unit having a bulky group exceeds 70% by mass, the hydroxyalkyl (meth)acrylate unit, the acidic group or the photopolymerizable functional group may not be sufficiently introduced, resulting in photosensitivity. The developability or film-forming property of the colored resin composition, or the flatness of the obtained colored layer becomes insufficient. The amount of the structural unit having a bulky group is more preferably 20 mass % or more and 60 mass % or less, and still more preferably 20 mass % or more and 55 mass % or less.

(構成主鏈之其他結構單元) 藉由在含有(甲基)丙烯酸羥烷基酯單元之共聚物之主鏈上包含既不具有官能基又不具有大體積基之結構單元,可調整物性,例如抑制鹼可溶性,提高溶劑溶解性,提高溶劑再溶解性等。 作為衍生出構成含有(甲基)丙烯酸羥烷基酯單元之共聚物之主鏈之其他結構單元的乙烯性不飽和單體,例如可使用(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等不具有官能基且具有低分子酯殘基之(甲基)丙烯酸酯。 (Other structural units that make up the main chain) By including a structural unit with neither functional group nor bulky group on the main chain of the copolymer containing hydroxyalkyl (meth)acrylate units, physical properties can be adjusted, such as inhibiting alkali solubility and improving solvent solubility , improve solvent re-solubility, etc. As the ethylenically unsaturated monomer from which other structural units constituting the main chain of the copolymer containing hydroxyalkyl (meth)acrylate units are derived, for example, methyl (meth)acrylate, ethyl (meth)acrylate can be used. (Meth)acrylate which has no functional group and has a low molecular ester residue, such as an ester.

(構成具有光聚合性官能基之側鏈之結構單元) 具有光聚合性官能基之側鏈可為僅由1個具有光聚合性官能基之結構單元所構成之側鏈結構,亦可具有由2個以上之結構單元連結而成之聚合物結構。於側鏈為具有1個單體之結構單元之側鏈結構時具有下述化學結構,該化學結構係含光聚合性官能基之單體所具有之與主鏈上之官能基反應而產生鍵之官能基產生了與主鏈鍵結之連結基。 作為具有光聚合性官能基、及與主鏈上之官能基反應而產生鍵之官能基之含光聚合性官能基之單體,例如可列舉:具有乙烯性不飽和鍵作為光聚合性官能基,且具有環氧基作為與主鏈上之官能基反應而產生鍵之官能基的(甲基)丙烯酸縮水甘油酯之類之化合物;及具有乙烯性不飽和鍵作為光聚合性官能基,且具有異氰酸基作為與主鏈上之官能基反應而產生鍵之官能基的化合物;等。 於使用具有光聚合性官能基及環氧基之單體之情形時,藉由使該單體與主鏈上之羧基反應,可形成具有光聚合性官能基之側鏈。於該情形時,在向含有(甲基)丙烯酸羥烷基酯單元之共聚物中導入光聚合性官能基之同時,主鏈上之羧基因與環氧基之反應而被消耗,從而酸值變小,因此含有(甲基)丙烯酸羥烷基酯單元之共聚物之光硬化性與顯影性以連動形式變化。因此,須考慮含有(甲基)丙烯酸羥烷基酯單元之共聚物之光硬化性與顯影性之平衡性來調節具有羧基之單體或由該單體所衍生之結構單元之量、與具有光聚合性官能基及環氧基之單體或由該單體所衍生之結構單元之量。 又,於使用具有光聚合性官能基及異氰酸基之單體之情形時,藉由使該單體與主鏈上之羥基反應,可形成具有光聚合性官能基之側鏈。 該等含光聚合性官能基之單體中,較佳為使用具有光聚合性官能基及環氧基之單體。於本發明中,就提高著色層之平坦性之觀點而言,重要的是含有(甲基)丙烯酸羥烷基酯單元之共聚物中之(甲基)丙烯酸羥烷基酯單元之量,但具有光聚合性官能基及環氧基之單體,其與羧基之反應性較高,幾乎不消耗含有(甲基)丙烯酸羥烷基酯單元之共聚物中之羥基,因此容易調節(甲基)丙烯酸羥烷基酯單元之量。 (Structural unit constituting a side chain having a photopolymerizable functional group) The side chain having a photopolymerizable functional group may have a side chain structure composed of only one structural unit having a photopolymerizable functional group, or may have a polymer structure formed by linking two or more structural units. When the side chain is a side chain structure having a structural unit of one monomer, it has the following chemical structure, and the chemical structure is that the photopolymerizable functional group-containing monomer reacts with the functional group on the main chain to generate a bond The functional group produces a linking group bonded to the main chain. Examples of the photopolymerizable functional group-containing monomer having a photopolymerizable functional group and a functional group that reacts with a functional group on the main chain to generate a bond include, for example, an ethylenically unsaturated bond as a photopolymerizable functional group. , and has an epoxy group as a functional group that reacts with a functional group on the main chain to generate a bond such as glycidyl (meth)acrylate; and has an ethylenically unsaturated bond as a photopolymerizable functional group, and Compounds having an isocyanate group as a functional group that reacts with a functional group on the main chain to generate a bond; and the like. When a monomer having a photopolymerizable functional group and an epoxy group is used, a side chain having a photopolymerizable functional group can be formed by reacting the monomer with the carboxyl group on the main chain. In this case, when the photopolymerizable functional group is introduced into the copolymer containing the hydroxyalkyl (meth)acrylate unit, the reaction between the carboxyl group on the main chain and the epoxy group is consumed, so that the acid value is Since it becomes smaller, the photocurability and developability of the copolymer containing a hydroxyalkyl (meth)acrylate unit change in a linked manner. Therefore, the amount of the monomer having a carboxyl group or a structural unit derived from the monomer, and the amount of the monomer having a carboxyl group or a structural unit derived from the The amount of monomers of photopolymerizable functional groups and epoxy groups or structural units derived from the monomers. Moreover, when using the monomer which has a photopolymerizable functional group and an isocyanate group, the side chain which has a photopolymerizable functional group can be formed by making this monomer react with the hydroxyl group on a main chain. Among these photopolymerizable functional group-containing monomers, a monomer having a photopolymerizable functional group and an epoxy group is preferably used. In the present invention, from the viewpoint of improving the flatness of the colored layer, what is important is the amount of hydroxyalkyl (meth)acrylate units in the copolymer containing hydroxyalkyl (meth)acrylate units, but Monomers with photopolymerizable functional groups and epoxy groups have high reactivity with carboxyl groups and hardly consume the hydroxyl groups in copolymers containing hydroxyalkyl (meth)acrylate units, so it is easy to adjust (methyl) ) amount of hydroxyalkyl acrylate units.

於含有(甲基)丙烯酸羥烷基酯單元之共聚物在側鏈具有乙烯性不飽和基之情形時,就獲得硬化膜之膜強度提高,耐顯影性提高,與基板之密接性優異等效果之觀點而言,乙烯性不飽和鍵當量較佳為100~2000之範圍,尤其較佳為140~1500之範圍。若該乙烯性不飽和鍵當量為100以上,則耐顯影性及密接性優異。又,若為2000以下,則可相對地增加上述具有酸性基之結構單元、及具有大體積基之結構單元等其他結構單元之比率,因此顯影性及耐熱性優異。 此處,乙烯性不飽和鍵當量係指含有(甲基)丙烯酸羥烷基酯單元之共聚物中之乙烯性不飽和鍵每1莫耳之重量平均分子量,由下述數學公式(1)表示。 When the copolymer containing a hydroxyalkyl (meth)acrylate unit has an ethylenically unsaturated group in the side chain, the film strength of the cured film is improved, the development resistance is improved, and the adhesion to the substrate is excellent. From a viewpoint, the range of 100-2000 is preferable, and, as for the ethylenically unsaturated bond equivalent, the range of 140-1500 is especially preferable. When this ethylenically unsaturated bond equivalent is 100 or more, it is excellent in development resistance and adhesiveness. Moreover, since the ratio of other structural units, such as the structural unit which has the said acidic group and the structural unit which has a bulky group, can be relatively increased as it is 2000 or less, it is excellent in developability and heat resistance. Here, the ethylenically unsaturated bond equivalent refers to the weight average molecular weight per 1 mole of the ethylenically unsaturated bond in the copolymer containing hydroxyalkyl (meth)acrylate units, and is represented by the following mathematical formula (1) .

數學公式(1) 乙烯性不飽和鍵當量(g/mol)=W(g)/M(mol) (數學公式(1)中,W表示含有(甲基)丙烯酸羥烷基酯單元之共聚物之質量(g),M表示含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之乙烯性雙鍵之莫耳數(mol)) Mathematical formula (1) Equivalent of ethylenically unsaturated bonds (g/mol)=W(g)/M(mol) (In the mathematical formula (1), W represents the mass (g) of the copolymer containing hydroxyalkyl (meth)acrylate units, and M represents the amount contained in the copolymer containing hydroxyalkyl (meth)acrylate units The number of moles of ethylenic double bond (mol)

上述乙烯性不飽和鍵當量例如可藉由以下方式算出,即,依據JIS K 0070:1992中所記載之碘值之試驗方法,測定含有(甲基)丙烯酸羥烷基酯單元之共聚物每1 g所含之乙烯性雙鍵之數。The above-mentioned ethylenically unsaturated bond equivalent can be calculated, for example, by measuring per 1 unit of the copolymer containing hydroxyalkyl (meth)acrylate units in accordance with the test method for iodine value described in JIS K 0070:1992. The number of ethylenic double bonds contained in g.

關於含有(甲基)丙烯酸羥烷基酯單元之共聚物中所含之具有光聚合性官能基之結構單元之量,相對於構成共聚物之結構單元之總量100質量%,較佳為2.5質量%以上35質量%以下。藉由使具有光聚合性官能基之結構單元之量處於上述範圍內,可提高含有(甲基)丙烯酸羥烷基酯單元之共聚物之光硬化性。 於具有光聚合性官能基之結構單元之量未達2.5質量%之情形時,可能導致無法充分地獲得含有(甲基)丙烯酸羥烷基酯單元之共聚物之光硬化性。另一方面,於具有光聚合性官能基之結構單元之量超過35質量%之情形時,會過度消耗主鏈之酸性基,而可能無法獲得充分之鹼可溶性。 具有光聚合性官能基之結構單元之量更佳為4質量%以上32質量%以下,進而較佳為5質量%以上31質量%以下。 The amount of the structural unit having a photopolymerizable functional group contained in the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 2.5 with respect to 100% by mass of the total amount of the structural units constituting the copolymer. Mass % or more and 35 mass % or less. By making the quantity of the structural unit which has a photopolymerizable functional group in the said range, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit can be improved. When the amount of the structural unit having a photopolymerizable functional group is less than 2.5% by mass, the photocurability of the copolymer containing a hydroxyalkyl (meth)acrylate unit may not be sufficiently obtained. On the other hand, when the quantity of the structural unit which has a photopolymerizable functional group exceeds 35 mass %, the acidic group of a main chain will be excessively consumed, and sufficient alkali solubility may not be acquired. The amount of the structural unit having a photopolymerizable functional group is more preferably 4 mass % or more and 32 mass % or less, and still more preferably 5 mass % or more and 31 mass % or less.

於本發明中,將含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量(Mw)設為11,000以上。藉由將含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量設為11,000以上,在對感光性著色樹脂之塗膜進行加熱乾燥時,可藉由含有(甲基)丙烯酸羥烷基酯單元之共聚物之分子量效應使已軟化之塗膜之黏度上升,而抑制塗膜之流動化。於含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量未達11,000之情形時,在進行加熱乾燥時,無法充分地抑制塗膜之流動化。 含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量並無特別限定,較佳為25,000以下。於含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量(Mw)超過25,000之情形時,感光性樹脂組合物之黏度變得過高,而可能與適合塗佈之黏度產生偏差。 含有(甲基)丙烯酸羥烷基酯單元之共聚物之重量平均分子量更佳為設為11,000以上20,000以下,進而較佳為設為11,000以上19,000以下。 In this invention, the weight average molecular weight (Mw) of the copolymer containing a hydroxyalkyl (meth)acrylate unit is made 11,000 or more. By setting the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit to 11,000 or more, when the coating film of the photosensitive colored resin is heated and dried, it can be The molecular weight effect of the copolymer of alkyl ester units increases the viscosity of the softened coating film and inhibits the fluidization of the coating film. When the weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is less than 11,000, the fluidization of the coating film cannot be sufficiently suppressed during heat drying. The weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is not particularly limited, but is preferably 25,000 or less. When the weight-average molecular weight (Mw) of the copolymer containing hydroxyalkyl (meth)acrylate units exceeds 25,000, the viscosity of the photosensitive resin composition becomes too high and may deviate from the viscosity suitable for coating . The weight average molecular weight of the copolymer containing a hydroxyalkyl (meth)acrylate unit is more preferably 11,000 or more and 20,000 or less, and still more preferably 11,000 or more and 19,000 or less.

再者,於本發明中,重量平均分子量(Mw)係藉由GPC(凝膠滲透層析法)而測定之值。測定係如下進行,即,使用Tosoh公司製造之HLC-8220GPC,採用添加有0.01莫耳/公升之溴化鋰之N-甲基吡咯啶酮作為溶出溶劑,採用Mw:8×10 5(F-80)、Mw:4×10 5(F-40)、Mw:2×10 5(F-20)、Mw:1×10 5(F-10)、Mw:4×10 4(F-4)、Mw:2×10 4(F-2)、Mw:5×10 3(A-5000)、Mw:2.5×10 3(A-2500)、Mw:1×10 3(A-1000)、Mw:5×10 2(A-500)(以上為Tosoh公司製造)作為校正曲線用聚苯乙烯標樣,採用TSK-GEL ALPHA-M×2根(Tosoh公司製造)作為測定管柱。 In addition, in this invention, the weight average molecular weight (Mw) is the value measured by GPC (gel permeation chromatography). The measurement was performed by using HLC-8220GPC manufactured by Tosoh Corporation, using N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide as the elution solvent, and using Mw: 8×10 5 (F-80) , Mw: 4×10 5 (F-40), Mw: 2×10 5 (F-20), Mw: 1×10 5 (F-10), Mw: 4×10 4 (F-4), Mw : 2×10 4 (F-2), Mw: 5×10 3 (A-5000), Mw: 2.5×10 3 (A-2500), Mw: 1×10 3 (A-1000), Mw: 5 ×10 2 (A-500) (manufactured by Tosoh Co., Ltd. above) was used as a polystyrene standard sample for the calibration curve, and TSK-GEL ALPHA-M×2 (manufactured by Tosoh Co., Ltd.) was used as a measurement column.

於本發明中,將含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值設為60 mgKOH/g以上130 mgKOH/g以下。藉由將含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值設為60 mgKOH/g以上,可對感光性著色樹脂之塗膜賦予充分之鹼可溶性,而使著色層之形狀平坦化之效果優異。另一方面,藉由將含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值設為130 mgKOH/g以下,於對塗膜進行顯影時可使基板上之顯影殘渣變少。 含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值較佳為65 mgKOH/g以上125 mgKOH/g以下,更佳為65 mgKOH/g以上110 mgKOH/g以下,進而更佳為70 mgKOH/g以上100 mgKOH/g以下。 於本發明之感光性著色樹脂組合物包含色澱色料作為色料之情形時,抑制顯影殘渣產生之效果較高,因此含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值可為100 mgKOH/g以上,亦可為110 mgKOH/g以上,亦可為120 mgKOH/g以上。含有(甲基)丙烯酸羥烷基酯單元之共聚物之酸值越高,越容易使著色層平坦化。 In this invention, the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is 60 mgKOH/g or more and 130 mgKOH/g or less. By setting the acid value of the copolymer containing hydroxyalkyl (meth)acrylate units to 60 mgKOH/g or more, sufficient alkali solubility can be imparted to the coating film of the photosensitive colored resin, and the shape of the colored layer can be flattened The effect of transformation is excellent. On the other hand, by making the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit into 130 mgKOH/g or less, when developing a coating film, the development residue on a board|substrate can be reduced. The acid value of the copolymer containing hydroxyalkyl (meth)acrylate units is preferably 65 mgKOH/g or more and 125 mgKOH/g or less, more preferably 65 mgKOH/g or more and 110 mgKOH/g or less, and still more preferably 70 More than mgKOH/g and less than 100 mgKOH/g. When the photosensitive coloring resin composition of the present invention contains a lake coloring material as a coloring material, the effect of suppressing the generation of development residues is high, so the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit can be improved. 100 mgKOH/g or more, 110 mgKOH/g or more, or 120 mgKOH/g or more. The higher the acid value of the copolymer containing a hydroxyalkyl (meth)acrylate unit, the easier it is to flatten the colored layer.

含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值較佳為50 mgKOH/g以上200 mgKOH/g以下。於含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值未達50 mgKOH/g之情形時,感光性著色樹脂組合物之塗膜之疏水性變得過高,可能導致顯影性變差。另一方面,於含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值超過200 mgKOH/g之情形時,感光性著色樹脂組合物之溶劑再溶解性變差,有塗佈性受損之虞。 含有(甲基)丙烯酸羥烷基酯單元之共聚物之羥值更佳為70 mgKOH/g以上190 mgKOH/g以下,進而較佳為80 mgKOH/g以上180 mgKOH/g以下。 The hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably 50 mgKOH/g or more and 200 mgKOH/g or less. When the hydroxyl value of the copolymer containing hydroxyalkyl (meth)acrylate units is less than 50 mgKOH/g, the hydrophobicity of the coating film of the photosensitive coloring resin composition becomes too high, which may lead to deterioration of developability. Difference. On the other hand, when the hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit exceeds 200 mgKOH/g, the solvent resolubility of the photosensitive coloring resin composition is deteriorated, resulting in poor coating properties. Danger of damage. The hydroxyl value of the copolymer containing a hydroxyalkyl (meth)acrylate unit is more preferably 70 mgKOH/g or more and 190 mgKOH/g or less, and still more preferably 80 mgKOH/g or more and 180 mgKOH/g or less.

含有(甲基)丙烯酸羥烷基酯單元之共聚物通常以溶解於溶劑中所得之清漆之狀態添加至本發明之彩色濾光片用感光性著色樹脂組合物中。雖無特別限定,但就容易獲得平坦性優異之著色層之觀點而言,含有(甲基)丙烯酸羥烷基酯單元之共聚物較佳為,於以固形物成分濃度成為60質量%之方式溶解於溶劑中所得之清漆之狀態下加熱至90℃時之黏度為500 mPa・s以上,更佳為600 mPa・s以上,進而更佳為700 mPa・s以上。另一方面,上述黏度可為10,000 mPa・s以下,亦可為9,000 mPa・s以下。若上述黏度為上述上限值以下。則感光性著色樹脂組合物容易乾燥,因此可提高彩色濾光片之生產性。 再者,關於用於使含有(甲基)丙烯酸羥烷基酯單元之共聚物溶解之溶劑,並無特別限定,例如可使用與本發明之彩色濾光片用感光性樹脂組合物中所含之溶劑相同者。 The copolymer containing a hydroxyalkyl (meth)acrylate unit is usually added to the photosensitive colored resin composition for color filters of the present invention in the state of a varnish obtained by being dissolved in a solvent. Although not particularly limited, the copolymer containing a hydroxyalkyl (meth)acrylate unit is preferably such that the solid content concentration becomes 60 mass % from the viewpoint of easily obtaining a colored layer excellent in flatness. The viscosity of the varnish obtained by dissolving it in a solvent when heated to 90°C is 500 mPa·s or more, more preferably 600 mPa·s or more, and still more preferably 700 mPa·s or more. On the other hand, the above-mentioned viscosity may be 10,000 mPa·s or less, or 9,000 mPa·s or less. If the said viscosity is below the said upper limit value. Since the photosensitive colored resin composition is easily dried, the productivity of the color filter can be improved. In addition, the solvent for dissolving the copolymer containing a hydroxyalkyl (meth)acrylate unit is not particularly limited, and for example, the solvent contained in the photosensitive resin composition for a color filter of the present invention can be used. the same solvent.

<其他黏合劑樹脂> 本發明之感光性著色樹脂組合物可與含有(甲基)丙烯酸羥烷基酯單元之共聚物組合含有其他黏合劑樹脂。作為其他黏合劑樹脂,可使用:具有自上述含有(甲基)丙烯酸羥烷基酯單元之共聚物之結構中去除(甲基)丙烯酸羥烷基酯單元後所得之結構之丙烯酸系樹脂、包含除該(甲基)丙烯酸羥烷基酯單元以外之結構單元及側鏈之丙烯酸系樹脂、苯乙烯-丙烯酸系樹脂、聚烯烴系樹脂等使含乙烯性不飽和鍵之單體聚合而獲得之感光性或非感光性之聚合物。進而,作為其他黏合劑樹脂,亦可使用為了形成彩色濾光片之著色層而一直用作黏合劑樹脂之聚合物、例如環氧系樹脂、胺基甲酸酯系樹脂、聚酯系樹脂、聚醯亞胺系樹脂、酚醛系樹脂等感光性或非感光性之樹脂。 <Other binder resins> The photosensitive colored resin composition of this invention may contain other binder resin in combination with the copolymer containing a hydroxyalkyl (meth)acrylate unit. As other binder resins, acrylic resins having a structure obtained by removing hydroxyalkyl (meth)acrylate units from the structure of the above-mentioned copolymer containing hydroxyalkyl (meth)acrylate units, including Structural units other than the hydroxyalkyl (meth)acrylate unit and side chain acrylic resins, styrene-acrylic resins, polyolefin resins, etc. are obtained by polymerizing ethylenically unsaturated bond-containing monomers Photosensitive or non-photosensitive polymers. Furthermore, as other binder resins, polymers which have been used as binder resins for forming colored layers of color filters, such as epoxy-based resins, urethane-based resins, polyester-based resins, Photosensitive or non-photosensitive resins such as polyimide resins and phenolic resins.

於本發明之感光性著色樹脂組合物中,相對於感光性著色樹脂組合物之固形物成分總量,黏合劑樹脂之含量通常為4質量%以上25質量%以下,較佳為5質量%以上22質量%以下,更佳為5質量%以上20質量%以下。 又,於本發明之感光性著色樹脂組合物中,相對於黏合劑樹脂之總量100質量份,含有(甲基)丙烯酸羥烷基酯單元之共聚物之含量通常為50質量份以上95質量份以下,較佳為60質量份以上92質量份以下,更佳為65質量份以上90質量份以下。 In the photosensitive colored resin composition of the present invention, the content of the binder resin is usually 4 mass % or more and 25 mass % or less, preferably 5 mass % or more with respect to the total solid content of the photosensitive coloring resin composition. 22 mass % or less, more preferably 5 mass % or more and 20 mass % or less. Moreover, in the photosensitive colored resin composition of the present invention, the content of the copolymer containing a hydroxyalkyl (meth)acrylate unit is usually 50 parts by mass or more and 95 parts by mass relative to 100 parts by mass of the total amount of the binder resin. part or less, preferably 60 parts by mass or more and 92 parts by mass or less, more preferably 65 parts by mass or more and 90 parts by mass or less.

[單體(光聚合性化合物)] 關於本發明之感光性著色樹脂組合物中所使用之作為光聚合性化合物之單體,只要能夠利用光起始劑進行聚合即可,並無特別限定,較佳為含有具有2個以上可聚合雙鍵之多官能單體。作為多官能單體,較佳為具有2個以上乙烯性不飽和雙鍵之多官能單體,尤其較佳為具有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。 作為多官能(甲基)丙烯酸酯,只要自先前公知之多官能(甲基)丙烯酸酯中進行適當選擇即可。作為具體例,例如可列舉日本專利特開2013-029832號公報中所記載之多官能(甲基)丙烯酸酯等。 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,作為多官能單體,較佳為具有3個(三官能)以上可聚合雙鍵者,例如可較佳地使用三價以上多元醇之聚(甲基)丙烯酸酯類或其等之二羧酸改性物。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、磷酸三(2-(甲基)丙烯醯氧基乙基)酯等。 若使用如磷酸三(2-(甲基)丙烯醯氧基乙基)酯之含磷原子之多官能(甲基)丙烯酸酯,則容易抑制色澱色料之褪色,容易提高後烘烤後之亮度,就該方面而言較佳。 該等多官能(甲基)丙烯酸酯可單獨使用一種,亦可組合兩種以上而使用。 [Monomer (photopolymerizable compound)] The monomer as a photopolymerizable compound used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized with a photoinitiator, but it is preferable to contain two or more polymerizable monomers. Multifunctional monomer with double bond. As the polyfunctional monomer, a polyfunctional monomer having two or more ethylenically unsaturated double bonds is preferred, and a polyfunctional (meth)acrylic acid having two or more acrylyl groups or methacrylyl groups is particularly preferred ester. The polyfunctional (meth)acrylate may be appropriately selected from previously known polyfunctional (meth)acrylates. As a specific example, the polyfunctional (meth)acrylate etc. which are described in Unexamined-Japanese-Patent No. 2013-029832 are mentioned, for example. Moreover, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), it is preferable that the polyfunctional monomer has three or more (trifunctional) polymerizable double bonds, such as Poly(meth)acrylates of trivalent or higher polyhydric alcohols or dicarboxylic acid-modified products thereof can be preferably used. Specifically, preferred are: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate succinic acid modified product, pentaerythritol tetra(meth)acrylate ) acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, succinic acid modified product of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Tris(2-(meth)acryloyloxyethyl)phosphate, etc. If a phosphorus atom-containing polyfunctional (meth)acrylate such as tris(2-(meth)acryloyloxyethyl)phosphate is used, it is easy to inhibit the fading of the lake color, and it is easy to improve the post-baking effect. The brightness is better in this respect. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

於本發明之感光性著色樹脂組合物中,就易使感光性著色樹脂組合物之塗膜之黏度變得適度,提高所獲得之著色層之平坦性之觀點而言,相對於單體之總量100質量份,多官能單體之含量較佳為90質量份以上,更佳為95質量份以上,尤佳為100質量份。In the photosensitive coloring resin composition of the present invention, the viscosity of the coating film of the photosensitive coloring resin composition is easily moderated and the flatness of the obtained coloring layer is improved. The content of the polyfunctional monomer is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, particularly preferably 100 parts by mass, based on 100 parts by mass.

於本發明之感光性著色樹脂組合物中,單體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%以上60質量%以下,更佳為10質量%以上50質量%以下。若單體之含量為上述下限值以上,則容易進行光硬化反應,藉此可抑制曝光部分在顯影時溶出,又,若單體之含量為上述上限值以下,則可提高鹼性顯影性。In the photosensitive colored resin composition of the present invention, the content of the monomer is not particularly limited, but is preferably 5% by mass or more and 60% by mass or less with respect to the total solid content of the photosensitive coloring resin composition, more preferably It is 10 mass % or more and 50 mass % or less. When the content of the monomer is equal to or more than the above-mentioned lower limit value, the photohardening reaction tends to proceed, whereby elution of the exposed portion during development can be suppressed, and when the content of the monomer is equal to or less than the above-mentioned upper limit value, the alkaline development can be improved. sex.

[光起始劑] 作為本發明之感光性著色樹脂組合物中所使用之光起始劑,並無特別限制,可自先前已知之各種起始劑中使用一種或組合兩種以上而使用。 作為光起始劑,例如可列舉:二苯甲酮、N,N-二甲基胺基二苯甲酮、4,4'-雙二乙基胺基二苯甲酮(例如Hicure ABP,川口藥品公司製造)、4-甲氧基-4'-二甲基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-萘并-1-基)-4,6-雙-三氯甲基-S-三𠯤等鹵甲基-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號公報等中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-(二甲基胺基)-1-(4-嗎啉基苯基)-1-丁酮(例如Irgacure 369,BASF公司製造)、2-(二甲基胺基)-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

Figure 110128859-A0304-12-01
等9-氧硫𠮿
Figure 110128859-A0304-12-01
類。 其中,就感度優異之觀點而言,本發明中所使用之光起始劑較佳為包含選自肟酯類及α-胺基酮類中之至少一種,就圖案形成時之線寬之調整及耐顯影性之觀點而言,較佳為α-胺基酮類。具有三級胺結構之α-胺基酮類在分子內具有作為氧猝滅劑之三級胺結構,因此起始劑所產生之自由基不易因氧而失活,可提高感度,就該方面而言較佳。 又,就抑制水斑,且提高感度之觀點而言,將肟酯類與α-胺基酮類加以組合而用作光起始劑亦較佳。再者,所謂水斑意指當使用使鹼性顯影性變高之成分時,於鹼性顯影後,利用純水進行沖洗後,產生如水滲入之痕跡。此種水斑會於後烘烤後消失,因此製品無問題,但會產生以下問題,即,顯影後在圖案化面之外觀檢查中會以不均異常之形式被檢測出,而無法區分正常品與異常品。因此,若在外觀檢查中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,從而成為問題。 又,就調整感度,抑制水斑,耐顯影性提高之觀點而言,較佳為將選自肟酯類及α-胺基酮類中之至少一種、與9-氧硫𠮿
Figure 110128859-A0304-12-01
類加以組合而作為光起始劑。 [Photoinitiator] The photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited, and may be used alone or in combination of two or more kinds of previously known various initiators. Examples of the photoinitiator include benzophenone, N,N-dimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone (for example, Hicure ABP, Kawaguchi Aromatic ketones such as pharmaceutical companies), 4-methoxy-4'-dimethylaminobenzophenone; benzoin ethers such as benzoin methyl ether; benzoins such as ethyl benzoin; 2-(o-chlorobenzene) yl)-4,5-phenylimidazole dimer and other biimidazoles; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyl Oxadiazole compounds; 2-(4-butoxy-naphtho-1-yl)-4,6-bis-trichloromethyl-S-tris-triss and other halomethyl-S-triss; 1, 2-Octanedione-1-[4-(phenylthio)-,2-(o-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzyl) Acetyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Publication No. 2010 - Oxime esters such as oxime ester-based photoinitiators described in Japanese Patent Publication No. 527339, Japanese Patent Publication No. 2010-527338, Japanese Patent Laid-Open No. 2013-041153, etc.; 2-methyl-1-(4 -Methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2-(dimethylamino)-1-(4-morpholine) phenyl)-1-butanone (for example, Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( α-amino ketones such as 4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF);
Figure 110128859-A0304-12-01
Wait for 9-oxysulfur 𠮿
Figure 110128859-A0304-12-01
kind. Among them, from the viewpoint of excellent sensitivity, the photoinitiator used in the present invention preferably contains at least one selected from the group consisting of oxime esters and α-amino ketones, and it is preferable to adjust the line width during pattern formation. From the viewpoint of development resistance, α-amino ketones are preferred. The α-amino ketones with tertiary amine structure have a tertiary amine structure as oxygen quencher in the molecule, so the free radicals generated by the initiator are not easily deactivated by oxygen, which can improve the sensitivity. is better. Moreover, from the viewpoint of suppressing water spots and improving sensitivity, it is also preferable to use oxime esters and α-amino ketones in combination as a photoinitiator. In addition, the so-called water spot means that when a component which increases the alkaline developability is used, after alkaline development, after rinsing with pure water, a trace like water infiltration occurs. Such water spots will disappear after post-baking, so there is no problem with the product, but there will be the following problems, that is, in the appearance inspection of the patterned surface after development, it will be detected in the form of uneven abnormality, and it is impossible to distinguish normal Goods and Unusual Goods. Therefore, when the inspection sensitivity of the inspection apparatus is lowered in the appearance inspection, the yield of the final color filter product is lowered as a result, which is a problem. In addition, from the viewpoint of adjusting sensitivity, suppressing water spots, and improving development resistance, it is preferable to combine at least one selected from oxime esters and α-amino ketones with 9-oxothiocyanate
Figure 110128859-A0304-12-01
are combined as photoinitiators.

關於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,只要無損本發明之效果,便無特別限制,相對於感光性著色樹脂組合物之固形物成分總量處於較佳為0.1質量%以上12.0質量%以下、更佳為1.0質量%以上8.0質量%以下之範圍內。若該含量為上述下限值以上,則光硬化充分地進行,抑制曝光部分在顯影時溶出,另一方面,若為上述上限值以下,則抑制所獲得之著色層之黃變,藉此可抑制亮度降低。The total content of the photoinitiators used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, and it is relatively high relative to the total solid content of the photosensitive colored resin composition. Preferably it is 0.1 mass % or more and 12.0 mass % or less, More preferably, it exists in the range of 1.0 mass % or more and 8.0 mass % or less. When the content is equal to or more than the above lower limit value, photohardening proceeds sufficiently, and elution of the exposed portion at the time of development is suppressed. On the other hand, if it is equal to or less than the above upper limit value, yellowing of the obtained colored layer is suppressed. Decrease in brightness can be suppressed.

[抗氧化劑] 就耐熱性提高,抑制色料之褪色,且亮度提高之觀點而言,本發明之感光性著色樹脂組合物較佳為進而含有抗氧化劑。本發明之感光性著色樹脂組合物藉由含有抗氧化劑,可於對硬化膜形成微孔時無損硬化性而控制微孔內之過度之自由基鏈鎖反應,因此可更容易地形成所需形狀之微孔。又,就容易獲得上述效果之觀點而言,抗氧化劑較佳為與肟酯系光起始劑組合而使用。 作為本發明中所使用之抗氧化劑,並無特別限定,只要自先前公知之抗氧化劑中適當選擇即可。作為抗氧化劑之具體例,例如可列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,就耐熱性之觀點、及使微孔之形狀變得良好之觀點而言,較佳為使用受阻酚系抗氧化劑。亦可為如國際公開第2014/021023號中所記載之潛在性抗氧化劑。 [Antioxidants] It is preferable that the photosensitive coloring resin composition of this invention further contains an antioxidant from the viewpoint of improving heat resistance, suppressing discoloration of a coloring material, and improving brightness. By containing an antioxidant, the photosensitive colored resin composition of the present invention can control the excessive free radical chain reaction in the micropores without damaging the curability when forming the micropores of the cured film, so that the desired shape can be formed more easily of micropores. Moreover, it is preferable to use an antioxidant in combination with an oxime ester type photoinitiator from a viewpoint of easily obtaining the said effect. The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from previously known antioxidants. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. From the viewpoint of heat resistance, and changing the shape of micropores From the viewpoint of being favorable, it is preferable to use a hindered phenol-based antioxidant. It can also be a latent antioxidant as described in International Publication No. 2014/021023.

作為受阻酚系抗氧化劑,例如可列舉: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公司製造)、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公司製造)、2,2'-亞甲基雙(6-第三丁基-4-甲基苯酚)(商品名:Sumilizer MDP-S,住友化學公司製造)、6,6'-硫代雙(2-第三丁基-4-甲基苯酚)(商品名:Irganox 1081,BASF公司製造)、3,5-二-第三丁基-4-羥基苄基膦酸二乙酯(商品名:Irgamod 195,BASF公司製造)等。 其中,就耐熱性及耐光性之觀點而言,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)。 Examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF Corporation), isocyanurate 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl) cyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4- Hydroxy-3,5-di-tert-butylbenzyl) mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methyl) phenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF Corporation ), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester (trade name: Irgamod 195, manufactured by BASF Corporation), and the like. Among them, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, BASF) is preferable from the viewpoint of heat resistance and light resistance manufactured by the company).

作為抗氧化劑之含量,相對於感光性著色樹脂組合物中之固形物成分總量,抗氧化劑較佳為0.1質量%以上10.0質量%以下,更佳為0.5質量%以上5.0質量%以下。若為上述下限值以上,則耐熱性及耐光性優異。另一方面,若為上述上限值以下,則可使感光性樹脂組合物成為高感度。As content of an antioxidant, 0.1 mass % or more and 10.0 mass % or less are preferable with respect to the solid content total amount in a photosensitive colored resin composition, and 0.5 mass % or more and 5.0 mass % or less are more preferable. If it is more than the said lower limit, it will be excellent in heat resistance and light resistance. On the other hand, if it is below the said upper limit, the photosensitive resin composition can be made into high sensitivity.

於將抗氧化劑與上述肟酯系光起始劑加以組合而使用之情形時,作為抗氧化劑之含量,相對於上述肟酯系光起始劑之合計量100質量份,抗氧化劑較佳為1質量份以上250質量份以下,更佳為3質量份以上80質量份以下,進而更佳為5質量份以上65質量份以下。若為上述範圍內,則上述組合之效果優異。When the antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, the content of the antioxidant is preferably 1 with respect to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator. The amount is not less than 250 parts by mass, more preferably not less than 3 parts by mass and not more than 80 parts by mass, and still more preferably not less than 5 parts by mass and not more than 65 parts by mass. Within the above-mentioned range, the effect of the above-mentioned combination is excellent.

[任意添加成分] 本發明之感光性著色樹脂組合物可視需要包含各種添加劑。作為添加劑,例如可列舉:巰基化合物、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、紫外線吸收劑、密接促進劑等。 作為界面活性劑及塑化劑之具體例,例如可列舉日本專利特開2013-029832號公報中所記載者。 [optional ingredients] The photosensitive colored resin composition of this invention may contain various additives as needed. As an additive, a mercapto compound, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, a defoaming agent, a silane coupling agent, a ultraviolet absorber, an adhesion promoter etc. are mentioned, for example. As a specific example of a surfactant and a plasticizer, the thing described in Unexamined-Japanese-Patent No. 2013-029832 is mentioned, for example.

[溶劑] 作為本發明中所使用之溶劑,只要為不與感光性著色樹脂組合物之各成分進行反應,而能夠使其等溶解或分散之有機溶劑即可,並無特別限定。溶劑可單獨使用一種或組合兩種以上而使用。 作為溶劑之具體例,例如可列舉: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、乙酸正丁酯、乙酸異丁酯、丁酸異丁酯、丁酸正丁酯、乳酸乙酯、乙酸環己酯等酯系溶劑;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)、卡必醇乙酸酯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。該等溶劑中,就其他成分之溶解性之觀點而言,適宜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,作為本發明中所使用之溶劑,就其他成分之溶解性或塗佈適應性之觀點而言,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)、卡必醇乙酸酯、乙酸-3-甲氧基-3-甲基丁酯、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一種以上。 [solvent] The solvent used in the present invention is not particularly limited as long as it is an organic solvent that can dissolve or disperse the components of the photosensitive colored resin composition without reacting with each other. A solvent can be used individually by 1 type or in combination of 2 or more types. Specific examples of the solvent include alcohol-based solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxy ethoxy ethanol, ethoxy ethoxy alcohol, and the like. Carbitol-based solvents such as ethyl alcohol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate , ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl lactate, cyclohexyl acetate and other ester solvents; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, cyclohexanone, and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, Glycol ether acetate solvents such as 3-methoxybutyl acetate and ethoxyethyl acetate; methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol Carbitol acetate solvents such as acetate (BCA) and carbitol acetate; diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol mono Methyl 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, etc. Alcohol ether solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other aprotic amide solvents; γ-butyrolactone and other lactones cyclic ether-based solvents such as tetrahydrofuran; unsaturated hydrocarbon-based solvents such as benzene, toluene, xylene, and naphthalene; saturated hydrocarbon-based solvents such as N-heptane, N-hexane, and N-octane; toluene and xylene Organic solvents such as aromatic hydrocarbons. Among these solvents, from the viewpoint of solubility of other components, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used. 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 from the viewpoint of solubility of other components or coating suitability. acetate (BCA), carbitol acetate, 3-methoxy-3-methylbutyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate more than one of the groups.

溶劑之含量並無特別限定,相對於感光性著色樹脂組合物之總量,較佳為75質量%以上95質量%以下,更佳為80質量%以上90質量%以下。藉由使感光性著色樹脂組合物中之溶劑之含量成為上述下限值以上,可提高其他成分之溶解性及塗佈適應性,另一方面,藉由使上述含量成為上述上限值以下,可使彩色濾光片之形成時所使用之感光性著色樹脂組合物之使用量變少。Although content of a solvent is not specifically limited, It is preferable that it is 75 mass % or more and 95 mass % or less with respect to the total amount of the photosensitive colored resin composition, More preferably, it is 80 mass % or more and 90 mass % or less. By making the content of the solvent in the photosensitive colored resin composition more than or equal to the above lower limit value, the solubility and coating suitability of other components can be improved, and on the other hand, by making the above content equal to or less than the above upper limit value, The usage-amount of the photosensitive coloring resin composition used at the time of formation of a color filter can be reduced.

II.彩色濾光片用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並無特別限定,例如可將上述色料、黏合劑樹脂、單體、光起始劑等各成分混合至溶劑中,使該等溶解或分散,藉此製造感光性著色樹脂組合物,較佳為藉由以下方式製造感光性著色樹脂組合物,即,預先製備使用分散劑使色料分散於溶劑中所獲得之色料分散液、或使色料溶解於溶劑中所獲得之色料溶液,使用公知之分散方法將該色料分散液或色料溶液、以及黏合劑樹脂、單體、光起始劑等除色料以外之感光性著色樹脂組合物之成分混合至溶劑中,使該等溶解或分散。 又,於使用兩種以上色料之情形時,可藉由以下方式製造感光性著色樹脂組合物,即,針對各個顏色之色料來準備色料分散液或色料溶液後,將各個色料分散液或色料溶液、以及黏合劑樹脂、光起始劑等除色料以外之感光性著色樹脂組合物之成分混合至溶劑中,使該等溶解或分散。 色料分散液及色料溶液係作為用於製備著色樹脂組合物之預製備物而使用。即,色料分散液及色料溶液係於製備著色樹脂組合物之準備階段進行預製備,P/V比、即(組合物中之色料成分質量)/(組合物中之色料成分以外之固形物成分質量)之比較高。具體而言,色料分散液及色料溶液之P/V比通常為1.0以上。 II. The manufacturing method of the photosensitive colored resin composition for color filters The manufacturing method of the photosensitive colored resin composition of the present invention is not particularly limited. For example, the above-mentioned components such as colorants, binder resins, monomers, and photoinitiators can be mixed into a solvent to dissolve or disperse them. In order to manufacture the photosensitive coloring resin composition by this, it is preferable to manufacture the photosensitive coloring resin composition by preliminarily preparing a color material dispersion liquid obtained by dispersing a color material in a solvent using a dispersant, or by making a color material dispersion liquid. The colorant solution obtained by dissolving the material in the solvent, the colorant dispersion or the colorant solution, and the photosensitive coloring resin other than the colorant such as the binder resin, monomer, photoinitiator, etc., are used by a known dispersion method. The components of the composition are mixed into a solvent to dissolve or disperse them. Furthermore, in the case of using two or more colorants, the photosensitive colored resin composition can be produced by preparing a colorant dispersion or a colorant solution for each color of the colorant, and then adding each colorant The dispersion liquid or the colorant solution, and the components of the photosensitive colored resin composition other than the colorant such as the binder resin and the photoinitiator are mixed into the solvent, and these are dissolved or dispersed. The colorant dispersion liquid and the colorant solution are used as pre-preparations for preparing the colored resin composition. That is, the colorant dispersion liquid and the colorant solution are pre-prepared in the preparation stage of preparing the colored resin composition, and the P/V ratio, that is, (the mass of the colorant component in the composition)/(the colorant component in the composition is not included) The solid content quality) is relatively high. Specifically, the P/V ratio of the colorant dispersion liquid and the colorant solution is usually 1.0 or more.

使用色料分散液而製造之本發明之感光性著色樹脂組合物含有分散劑。含有色澱色料或顏料之本發明之感光性著色樹脂組合物較佳為使用分散有色澱色料或顏料之色料分散液進行製造,因此較佳為含有分散劑。 以下,對本發明之感光性著色樹脂組合物之製造中所使用之色料分散液進行詳細說明。 本發明中所使用之色料分散液包含溶劑、分散劑、及利用該分散劑而分散於該溶劑中之上述色料,亦可視需要進而包含分散助劑等其他成分。 The photosensitive colored resin composition of the present invention produced using the colorant dispersion liquid contains a dispersant. The photosensitive colored resin composition of the present invention containing a lake color material or a pigment is preferably produced using a color material dispersion liquid in which a lake color material or a pigment is dispersed, and therefore preferably contains a dispersant. Hereinafter, the color material dispersion liquid used for manufacture of the photosensitive colored resin composition of this invention is demonstrated in detail. The colorant dispersion liquid used in the present invention includes a solvent, a dispersant, and the above-mentioned colorant dispersed in the solvent by using the dispersant, and may further include other components such as a dispersing aid as required.

[分散劑] 作為分散劑,可自先前被用作分散劑者中進行適當選擇而使用。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、氟系等界面活性劑。界面活性劑中,就能夠均勻且微細地分散之觀點而言,較佳為高分子界面活性劑(高分子分散劑)。 作為高分子分散劑,例如可列舉: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)烷胺鹽類;含羥基之聚丙烯酸酯等含羥基之不飽和羧酸酯之(共)聚合物或其等之改性物;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)與含游離羧基之聚酯之反應所獲得之醯胺或其等之鹼);聚烯丙胺衍生物(藉由使聚烯丙胺、與選自具有游離羧基之聚酯、聚醯胺或酯與醯胺之共縮合物(聚酯醯胺)之三種化合物中之一種以上化合物進行反應而獲得之反應產物)等。 [Dispersant] As a dispersing agent, it can select suitably from those previously used as a dispersing agent, and can be used. As the dispersing agent, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferred from the viewpoint of being able to uniformly and finely disperse. Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts and (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 unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or their modifications; polyurethanes; unsaturated polyacrylates amides; polysiloxanes; long-chain polyaminoamide phosphates; polyethylenimine derivatives (by reaction of poly(lower alkyleneimine) with polyesters containing free carboxyl groups) The obtained amides or their equivalent bases); polyallylamine derivatives (by making polyallylamine, and selected from polyesters with free carboxyl groups, polyamides or co-condensates of esters and amides (polyesters). The reaction product obtained by reacting one or more of the three compounds of amide) and the like.

分散劑可根據色料之種類而適當地選擇分散性良好者進行使用,並無特別限定,但於使上述通式(1)或(2)所表示之色澱色料、或者上述通式(5)所表示之二苯并哌喃系染料之金屬色澱色料進行分散之情形、以及使該等色澱色料與二苯并哌喃系染料等染料或C.I.顏料藍15:6等顏料進行共分散之情形時,作為分散劑,較佳為使用作為酸性高分子分散劑之酸性分散劑。再者,於本發明中,染料可溶解於溶劑中而使用。 於使顏料分散之情形時,較佳為根據顏料之種類使用選自由酸性或鹼性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一種,更佳為使用酸性或鹼性高分子分散劑。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高分子分散劑之鹼性分散劑。 作為用於使色澱色料分散之酸性分散劑,例如適宜使用選自具有下述通式(I)所表示之結構單元之聚合物、及下述含羧基之嵌段共聚物中之至少一種。作為用於使顏料分散之酸性分散劑,例如適宜使用含羧基之嵌段共聚物。 作為鹼性分散劑,例如適宜使用選自由下述聚合物所組成之群中之至少一種:包含具有三級胺之重複單元之聚合物、及由包含具有三級胺之重複單元之聚合物中的胺基中之至少一部分與有機酸化合物形成鹽所得之鹽型聚合物。 胺基甲酸酯系分散劑係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,例如適宜使用1分子中具有2個以上異氰酸基之多異氰酸酯類、與單末端或兩末端具有羥基之聚酯類之反應產物。 The dispersant can be appropriately selected and used according to the type of colorant with good dispersibility, and is not particularly limited. 5) The situation of dispersing the metallic lake coloring materials of the dibenzopyran-based dyes represented, and making these lake coloring materials and dyes such as dibenzopyran-based dyes or pigments such as C.I. Pigment Blue 15:6 In the case of co-dispersion, it is preferable to use an acidic dispersant which is an acidic polymer dispersant as a dispersant. In addition, in this invention, a dye can be melt|dissolved in a solvent, and can be used. In the case of dispersing the pigment, it is preferable to use at least one selected from the group consisting of an acidic or basic polymer dispersant and a urethane-based dispersant according to the type of the pigment, and it is more preferable to use an acidic or basic polymer dispersant. Alkaline polymer dispersant. 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 polymer dispersant Alkaline dispersing agent. As the acidic dispersant for dispersing the lake coloring material, for example, at least one selected from the group consisting of a polymer having a structural unit represented by the following general formula (I) and a carboxyl group-containing block copolymer described below is suitably used. . As an acidic dispersing agent for dispersing a pigment, for example, a carboxyl group-containing block copolymer is suitably used. As the basic dispersant, for example, at least one selected from the group consisting of polymers comprising repeating units having tertiary amines and polymers comprising repeating units having tertiary amines are suitably used. A salt-type polymer in which at least a part of the amine group forms a salt with an organic acid compound. 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 polyisocyanates having two or more isocyanate groups in one molecule and polyesters having hydroxyl groups at one or both ends is 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色澱色料之分散劑,尤其可較佳地用作上述通式(1)或通式(2)所表示之色澱色料之分散劑。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,則可提高色澱色料之分散性與耐熱性,可抑制加熱後之色澱色料之色度變化。又,於併用色澱色料與顏料作為色料之情形時,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,可提高顏料之分散性及保存穩定性,可形成基板密接性與塗膜均勻性得到提高之著色層。 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聚合物,因此推定如下: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 ))對經微粒子化之色料之表面具有較強之吸附力。又,推定,若色料表面處於被酸性磷化合物基及其鹽之至少一種被覆之狀態下,則抑制過氧自由基等活性氧對色澱色料之色素骨架之攻擊(奪氫或取代反應等),從而抑制色澱色料之劣化(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 dispersant for lake pigments, particularly preferably It can be used as a dispersant for the lake coloring material represented by the above general formula (1) or general formula (2). 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 lake color material can be improved, and the chromaticity change of the lake color material after heating can be suppressed . In addition, when a lake colorant and a pigment are used in combination as a colorant, by using a polymer having a structural unit represented by the following general formula (I) as a dispersant, the dispersibility and storage stability of the pigment can be improved , a coloring layer with improved substrate adhesion and coating film uniformity can be formed. The polymer having the structural unit represented by the following general formula (I) is an ethylenically unsaturated monomer polymer, so it is presumed as follows: the heat resistance of the skeleton is higher than that of the polyether-based or polyester-based polymer, And there are a plurality of acidic phosphorus compound groups (-P(=O)(-R 12 )(OH)) and their salts (-P(=O)(-R 12 )(O - X + )) has a strong adsorption force on the surface of the micronized colorant. In addition, it is presumed that if the surface of the colorant is in a state of being covered by at least one of the acidic phosphorus compound group and its salt, the attack (hydrogen abstraction or substitution reaction) of the pigment skeleton of the lake coloring material by reactive oxygen species such as peroxy radicals is suppressed. etc.), thereby suppressing the deterioration (oxidative deterioration) of the lake color material.

[化14]

Figure 02_image031
(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分別獨立地為氫原子或甲基,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分別獨立地為氫原子、烴基、或具有選自醚鍵及酯鍵中之一種以上之烴基,R 17及R 19可彼此鍵結而形成環結構;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一種以上之烴基;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 14]
Figure 02_image031
(In the 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 each independently a hydrogen atom or a methyl group, and R 15 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO, -CO-CH=CH 2 , -CO-C(CH 3 )=CH 2 or a valent group represented by -CH 2 COOR 23 , R 23 is a hydrogen atom or the number of carbon atoms is 1 or more and 5 or less 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, 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 may further have a substituent R 24 , R 24 is a hydrocarbon group, or has one or more selected from ether bonds and ester bonds The above hydrocarbon group may have a substituent; X represents a hydrogen atom or an organic cation; x1 represents an integer from 1 to 18, y1 represents an integer from 1 to 5, and z1 represents an integer from 1 to 18)

於通式(I)中,L 1 1為直接鍵或二價連結基。此處,所謂L 1 1為直接鍵,意指磷原子未經由連結基而直接鍵結於主鏈骨架之碳原子。 作為L 1 1中之二價連結基,只要能夠將主鏈骨架之碳原子、與磷原子加以連結,便無特別限制。作為L 1 1中之二價連結基,例如可列舉: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)、及其等之組合等。再者,於本發明中,二價連結基之鍵之朝向隨意。即,於二價連結基中包含-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,反之,亦可為-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 1 1 is a direct bond or a divalent linking group. Here, L 1 1 is a direct bond, meaning that the phosphorus atom is directly bonded to the carbon atom of the main chain skeleton without a linking group. The divalent linking group in L 1 1 is not particularly limited as long as it can link the carbon atom and the phosphorus atom of the main chain skeleton. Examples of the divalent linking group in L 1 1 include linear, branched or cyclic alkylene, linear, branched or cyclic alkylene having a hydroxyl group, aryl, -CONH - group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof and the like. Furthermore, in the present invention, the direction of the bond of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be the carbon atom side of the main chain and -NH may be the phosphorus atom side of the side chain, and conversely, -NH may be the carbon atom side of the main chain. atom side and -CO is the phosphorus atom side of the side chain.

其中,就分散性之觀點而言,通式(I)中之L 11較佳為包含-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,L 11較佳為-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分別獨立地為氫原子、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, from the viewpoint 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, L 11 is preferably a -COO-L 11 '- group (here, L 11 ' is one or more carbon atoms which may have a hydroxyl group) 8 or less 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 each independently a hydrogen atom, a methyl group, or a hydroxyl group; x represents an integer of 1 or more and 18 or less, and y represents an integer of 1 or more and 5 or less , z represents an integer of 1 or more and 18 or less, and w represents an integer of 1 or more and 18 or less).

L 1 1'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,一部分氫亦可被取代為羥基。 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。 In L 1 1 ', the alkylene group having 1 to 8 carbon atoms may be any of linear, branched, or cyclic, such as methylene, ethylidene, trimethylene, For propylidene groups, various butylene groups, various pentylene groups, various hexylene groups, various octylidene groups, etc., a part of hydrogen can also be substituted into hydroxyl groups. x is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, y is 1 or more and 5 or less, preferably 1 or more and 4 or less, more preferably 2 or 3. z is an integer of 1 or more and 18 or less, preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less. w is an integer of 1 or more and 18 or less, and preferably an integer of 1 or more and 4 or less.

作為通式(I)中之L 1 1之較佳之具體例,例如可列舉-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,但並不限於其等。 Preferable specific examples of L 1 1 in the general formula (I) include -COO-CH 2 CH(OH)CH 2 -O-, -COO-CH 2 CH 2 -O-CH 2 CH(OH), for example )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 1 2中之烴基,例如可列舉: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,例如可列舉: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、低級烷基取代之金剛烷基等。 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,例如可列舉:乙烯基、烯丙基、丙烯基等。烯基之雙鍵之位置並無限定,但就所獲得之聚合物之反應性之觀點而言,較佳為在烯基之末端存在雙鍵。 作為芳基,可列舉苯基、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,可列舉苄基、苯乙基、萘基甲基、聯苯甲基等,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,可列舉F、Cl、Br等鹵素原子、硝基等。 又,作為上述芳基或芳烷基等芳香環之取代基,除碳數為1個以上4個以下之直鏈狀、支鏈狀之烷基以外,還可列舉烯基、硝基、鹵素原子等。 再者,上述較佳之碳數中不包含取代基之碳數。 上述R 1 2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 1 5~R 22中之烴基,例如可列舉與上述R 1 2中之烴基相同者。 Examples of the hydrocarbon group in R 1 2 include 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. The above-mentioned alkyl group having 1 or more carbon atoms and 18 or less carbon atoms may be any of linear, branched and cyclic, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl , cyclopentyl, cyclohexyl, adamantyl, isosyl, dicyclopentyl, adamantyl, adamantyl substituted by lower alkyl, etc. The alkenyl group having 2 or more carbon atoms and 18 or less 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 from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond exists at the terminal of the alkenyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, and the like, which may further have a substituent. The number of carbon atoms in the aryl group is preferably 6 or more and 24 or less, and more preferably 6 or more and 12 or less. 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 7 or more and 20 or less, and more preferably 7 or more and 14 or less. The above-mentioned alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, and a nitro group. Further, as the substituent of the aromatic ring such as the above-mentioned aryl group or aralkyl group, in addition to the linear and branched alkyl groups having 1 to 4 or less carbon atoms, alkenyl groups, nitro groups and halogens can also be mentioned. atom etc. In addition, the carbon number of the substituent is not included in the above-mentioned preferable carbon number. In the above R 1 2 , x1 is the same as the above x, y1 is the same as the above y, and z1 is the same as the above z. As the hydrocarbon group in R 1 5 to R 22 , for example, the same ones as the hydrocarbon group in the above-mentioned R 1 2 can be mentioned.

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一種以上之烴基為-R'-O-R''、-R'-(C=O)-O-R''、或-R'-O-(C=O)-R''(R'及R''為烴基、或者以醚鍵及酯鍵之至少1個鍵結有烴基之基)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況,可列舉烷基、烯基、芳烷基、芳基,作為烴基為二價之情況,可列舉伸烷基、伸烯基、伸芳基、及其等之組合基。 Among R 17 , R 18 , R 19 , R 20 , R 21 and R 22 , the hydrocarbon groups having one or more selected from ether bonds and ester bonds are -R'-O-R'', -R'-(C =O)-O-R'', or -R'-O-(C=O)-R''(R' and R'' are hydrocarbon groups, or have at least one of ether bond and ester bond. A base represented by a hydrocarbon group). One group may have two or more ether bonds and ester bonds. When the hydrocarbon group is monovalent, an alkyl group, an alkenyl group, an aralkyl group, and an aryl group can be cited, and when the hydrocarbon group is divalent, an alkylene group, an alkenylene group, an aryl group, and a combination thereof can be cited base.

於R 17與R 19鍵結而形成環結構之情形時,構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。 關於取代基R 24中之烴基、或具有選自醚鍵及酯鍵中之一種以上之烴基,可設為與上述R 17、R 18、R 19、R 20、R 21及R 22中之烴基、或具有選自醚鍵及酯鍵中之一種以上之烴基相同者。 When R 17 and R 19 are bonded to form a ring structure, the number of carbon atoms constituting the ring structure is preferably 5 or more and 8 or less, more preferably 6, that is, a 6-membered ring, preferably a cyclohexane ring. The hydrocarbon group in the substituent R 24 or the hydrocarbon group having one or more selected from ether bonds and ester bonds can be the same as the hydrocarbon groups in the above-mentioned R 17 , R 18 , R 19 , R 20 , R 21 and R 22 . , or the same one having one or more hydrocarbon groups selected from ether bonds and ester bonds.

就所分散之粒子之分散性及分散穩定性優異之觀點而言,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,更佳為上述R 12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,R 13及R 14分別獨立地為氫原子或甲基,且R 15為-CO-CH=CH 2或-CO-C(CH 3)=CH 2,其中,R 12更佳為可具有取代基之芳基、乙烯基、甲基及羥基。 From the viewpoint of excellent dispersibility and dispersion stability of the dispersed particles, the above 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, the above R 12 is a hydroxyl group, a methyl group, an ethyl group, a vinyl group, or an aryl group which may have a substituent or aralkyl, vinyl, allyl, -[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 , 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 , wherein, More preferably, R 12 is an aryl group, a vinyl group, a methyl group and a hydroxyl group which may have a substituent.

又,就耐鹼性提高之觀點而言,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,不易水解,因此推定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觀點而言,較佳為R 12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,R 13及R 14分別獨立地為氫原子或甲基,且R 1 5為-CO-CH=CH 2或-CO-C(CH 3)=CH 2。其中,就分散性之觀點而言,R 12更佳為可具有取代基之芳基。 Furthermore, from the viewpoint 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 valent base. In the case of having a structure in which a carbon atom is directly bonded to a phosphorus atom, it is unlikely to be hydrolyzed, so it is presumed that a resin layer excellent in alkali resistance can be formed. Among them, R 12 is preferably a methyl group, an ethyl group, an optionally substituted aryl group or an aralkyl group, from the viewpoints of excellent alkali resistance and excellent dispersibility and dispersion stability of the dispersed particles, A valent group represented by vinyl, allyl, -[CH(R 13 )-CH(R 14 )-O] x1 -R 15 , or -[(CH 2 ) y1 -O] z1 -R 15 , 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, from the viewpoint 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,例如可列舉: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,就分散性及鹼性顯影性之觀點而言,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雙鍵之情形時,可賦予硬化性,就該方面而言較佳。 Moreover, in general formula (I), X represents a hydrogen atom or an organic cation. Organic cations refer to those in which the cationic moiety 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 trialkylpernium cations. Phosphonium cations such as permanium cations, tetraalkylphosphonium cations, etc. Among them, from the viewpoint of dispersibility and alkali developability, protonated nitrogen-containing organic cations are preferred. Among them, when the organic cation has an ethylenically unsaturated double bond, sclerosing property can be imparted, which is preferable in this respect.

通式(I)所表示之結構單元可於聚合物中單獨包含一種,亦可包含兩種以上。The structural unit represented by the general formula (I) may be contained alone in the polymer, or two or more may be contained.

於聚合物中,可包含通式(I)所表示之結構單元中X為氫原子之結構單元、與X為有機陽離子之結構單元此兩結構單元。於包含該兩結構單元之情形時,只要發揮出良好之分散性、及分散穩定性即可,並無特別限制,相對於通式(I)所表示之結構單元之合計結構單元數,X為有機陽離子之結構單元數之比率較佳為0莫耳%以上50莫耳%以下。In the polymer, in the structural unit represented by the general formula (I), two structural units, in which X is a hydrogen atom and a structural unit in which X is an organic cation, can be included. In the case of including the two structural units, there is no particular limitation as long as good dispersibility and dispersion stability are exhibited, and X is the total number of structural units of the structural units represented by the general formula (I). The ratio of the number of structural units of the organic cation is preferably 0 mol % or more and 50 mol % or less.

關於具有通式(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號公報來合成具有通式(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下述聚合物,該聚合物係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,且酸性磷化合物基之至少一部分可形成鹽。There is no particular limitation on the synthesis method of the polymer having the structural unit represented by the general formula (I). polymer. The polymer having the structural unit represented by the general formula (I) is preferably a polymer having at least one of an epoxy group and a cyclic ether group in the side chain, and an acidic phosphorus compound. The reaction product, and at least a portion of the acidic phosphorus compound group may form a salt.

本發明之實施方式中,就分散性之觀點而言,具有通式(I)所表示之結構單元之聚合物較佳為進而具有溶劑親和性部位。作為此種聚合物,就分散性、及保存穩定性優異,即便在長期保管後亦可形成高對比度之塗膜之觀點而言,其中,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、或者具有上述通式(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 the embodiment of the present invention, from the viewpoint of dispersibility, the polymer having the structural unit represented by the general formula (I) preferably further has a solvent-affinity site. Such a polymer is excellent in dispersibility and storage stability, and from the viewpoint of forming a high-contrast coating film even after long-term storage, it is preferable to have a structure represented by the above-mentioned general formula (I). unit, a graft copolymer with a structural unit represented by the following general formula (II), or a graft copolymer having a structural unit represented by the above general formula (I) and a structural unit represented by the following general formula (III) segmented copolymer.

[化15]

Figure 02_image033
(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分別獨立地為氫原子或甲基,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 15]
Figure 02_image033
(In general formula (II), L 21 represents a direct bond or a divalent linking group, R 25 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); General formula In (III), R 26 is a hydrogen atom or a methyl group, and R 27 is a hydrocarbon group, -[CH(R 28 )-CH(R 29 )-O] x2 -R 30 , -[(CH 2 ) y2 -O] A valent group represented by 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 independently a hydrogen atom or a methyl group, R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or a valent group represented by -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 One valent group represented, R 30 " is an alkyl group with more than 1 carbon number but less than 18, R 31 is a hydrogen atom or an alkyl group with more than 1 carbon number but less than 5; the above-mentioned hydrocarbon group may have a substituent; x2 and x2' represent integers from 1 to 18, y2 and y2' represent integers from 1 to 5 and below, z2 and z2' represent integers from 1 to 18)

[化16]

Figure 02_image035
(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分別獨立地為氫原子或甲基,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 16]
Figure 02_image035
(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 A valent group represented by -O] z3 - R36 , -[CO-( CH2 ) y3 -O] z3 - R36 , -CO- OR37 or -O-CO- R38 , R34 and R35 each independently a hydrogen atom or a methyl group, R 36 is a hydrogen atom, a hydrocarbon group, a valent group represented by -CHO, -CH 2 CHO or -CH 2 COOR 39 , R 37 is a hydrocarbon 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 group, R 38 is an alkyl group with 1 to 18 carbon atoms, R 39 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and the above hydrocarbon group may have a substituent; n represents 5 or more and 200 or less x3 and x4 represent integers between 1 and 18, y3 and y4 represent integers between 1 and 5, and z3 and z4 represent integers between 1 and 18)

(接枝共聚物) 關於作為酸性分散劑而較佳之接枝共聚物,例如可列舉具有上述通式(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。 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雙鍵之碳原子與聚合物鏈加以連結,便無特別限制。作為L 21中之二價連結基,例如可列舉與上述L 11中之二價連結基相同者。 (Graft Copolymer) As an acidic dispersant, a preferred graft copolymer includes, for example, a graft copolymer having a structural unit represented by the above-mentioned general formula (I) and a structural unit represented by the above-mentioned general formula (II). copolymer. In the above general formula (II), L 21 is a direct bond or a divalent linking group. The divalent linking group in L 21 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond to the polymer chain. As a divalent linking group in L21 , the thing similar to the divalent linking group in said L11 is mentioned, for example.

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。 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。關於其等,例如可列舉與上述之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 R 33 is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group . As for these, for example, the same thing as the above-mentioned R 12 can be mentioned.

R 36較佳為氫原子、或者碳數為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。 關於上述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,可列舉與上述R 12相同者。 關於上述R 38及R 39中之烷基,可列舉與上述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,還可列舉烯基、硝基、F、Cl、Br等鹵素原子等。 再者,上述較佳之碳數中不包含取代基之碳數。 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 a valent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH 2 CHO or -CH 2 COOR 39 , and R 37 is preferably an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R 34 )-CH(R 35 )-O] x4 -R 36 , -[(CH 2 ) y4 -O] z4 -R 36 , a valent group represented by -[CO-(CH 2 ) y4 -O] z4 -R 36 . R 38 is an alkyl group having 1 to 18 carbon atoms, and R 39 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As for the alkyl group, aralkyl group and aryl group having 1 or more and 18 or less carbon atoms in the above R 36 and R 37 , the same ones as those of the above R 12 can be exemplified. The alkyl group in the above-mentioned R 38 and R 39 is the same as that of the above-mentioned R 12 . When the above-mentioned R 36 , R 37 and R 39 are groups having an aromatic ring, the aromatic ring may further have a substituent. The substituents include, for example, alkenyl groups, nitro groups, halogen atoms such as F, Cl, and Br, in addition to linear, branched, and cyclic alkyl groups having 1 or more carbon atoms and 5 or less carbon atoms. . In addition, the carbon number of the substituent is not included in the above-mentioned preferable carbon number. In the above R 33 and R 37 , x3 and x4 are the same as the above x, y3 and y4 are the same as the above y, and z3 and z4 are the same as the above z.

進而,上述R 33、R 36、R 37、R 38及R 39可於不妨礙上述接枝共聚物之分散性能等之範圍內,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取代。又,亦可於合成具有該等取代基之接枝共聚物後,使具有與該取代基反應之官能基及聚合性基之化合物進行反應而加成有聚合性基。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,或者使具有異氰酸基之接枝共聚物與(甲基)丙烯酸羥基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 alkoxy group, hydroxyl group, carboxyl group, amino group, epoxy group within the range that does not hinder the dispersibility of the above-mentioned graft copolymer. , isocyanate group, hydrogen bond forming group and other substituent groups. Moreover, after synthesizing the graft copolymer having these substituents, a polymerizable group may be added by reacting a compound having a functional group reacting with the substituent and a polymerizable 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 to obtain addition polymerizable properties. base.

具有通式(IV)所表示之結構單元之聚合物鏈較佳為具有上述結構單元中之源自(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)丙烯酸金剛烷酯、苯乙烯、α-甲基苯乙烯、乙烯基環己烷等之結構單元。然而,並不限於其等。The polymer chain having the structural unit represented by the general formula (IV) is preferably derived from methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate among the above-mentioned structural units , n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxy (meth)acrylate Ethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isopropyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylate Structural units of adamantyl acrylate, styrene, α-methylstyrene, vinylcyclohexane, etc. However, it is not limited to these and the like.

於本發明之實施方式中,作為上述R 33及R 37,其中,較佳為使用與有機溶劑之溶解性優異者,只要根據用於色料分散液中之有機溶劑進行適當選擇即可。具體而言,例如於使用作為色料分散液之有機溶劑而普遍使用之醚醇乙酸酯系、醚系、酯系等有機溶劑作為有機溶劑之情形時,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,將上述R 33及R 37如此設定之原因在於,包含上述R 33及R 37之結構單元相對於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相對於色料等粒子具有較高之吸附性,藉此可使色料等粒子之分散性、及穩定性變得尤其優異。 In the embodiment of the present invention, among the above R 33 and R 37 , those having excellent solubility in organic solvents are preferably used, and may be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when organic solvents such as ether alcohol acetates, ethers, and esters, which are commonly used as organic solvents for colorant dispersions, are used as the organic solvent, methyl and ethyl are preferred. , isobutyl, n-butyl, 2-ethylhexyl, 2-ethoxyethyl, cyclohexyl, benzyl, etc. Here, the reason why the above-mentioned R 33 and R 37 are set as such is that the structural unit including the above-mentioned R 33 and R 37 is soluble in the above-mentioned organic solvent, and the acid phosphorus compound group of the above-mentioned monomer and the site of the salt thereof are relatively soluble in the above-mentioned organic solvent. Particles such as colorants have high adsorption properties, whereby the dispersibility and stability of particles such as colorants 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,可保持作為分散劑之充分之立體排斥效應,並且亦可抑制因立體效應而使色料等粒子之分散所需之時間增大。The weight average molecular weight of the polymer chain in the polymer is preferably within the range of 500 or more and 15,000 or less, more preferably within the range of 1,000 or more and 8,000 or less. By being in the said range, the sufficient steric repulsion effect as a dispersing agent can be maintained, and the time required for dispersion|distribution of the particle|grains, such as a colorant, by a steric effect can also be suppressed.

又,關於Polymer中之聚合物鏈,其標準較佳為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。In addition, regarding the polymer chain in the polymer, the standard is preferably that the solubility at 23° C. is 50 (g/100 g solvent) or more 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)所表示之結構單元中所含之聚合物鏈於接枝共聚物中可為單獨一種,亦可混合兩種以上。The above-mentioned polymer chain may be a homopolymer or a copolymer. In addition, the polymer chain 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所有結構單元,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%以下之比率被包含,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,則接枝共聚物中之與粒子之親和性部位之比率變得適當,且可抑制對有機溶劑之溶解性之降低,因此對色料等粒子之吸附性變得良好,可獲得優異分散性、及分散穩定性。又,上述接枝共聚物之酸性磷化合物基可穩定地局部存在於色料周邊,因此可獲得耐熱性及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所有結構單元,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%以下之比率被包含,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率係自合成共聚物時之添加量而算出。 The structural unit represented by the general formula (I) is preferably contained in a ratio of 3 mass % or more and 80 mass % or less in total, more preferably 10 mass % or more with respect to all the structural units of the graft copolymer. 70 mass % or less, more preferably 20 mass % or more and 60 mass % or less. If the total content of the structural units represented by the general formula (I) in the graft copolymer is within the above-mentioned range, the ratio of the affinity sites to the particles in the graft copolymer becomes appropriate, and the organic solvent can be suppressed. As the solubility decreases, the adsorption to particles such as colorants becomes good, and excellent dispersibility and dispersion stability can be obtained. In addition, since the acidic phosphorus compound group of the graft copolymer can be stably localized in the periphery of the colorant, a color filter excellent in heat resistance and contrast can be obtained. On the other hand, the structural unit represented by the general formula (II) is preferably contained in a ratio of 20% by mass to 97% by mass, more preferably 25% by mass, with respect to all the structural units of the graft copolymer. More than 95 mass % or less, more preferably 40 mass % or more and 90 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,可使色料等粒子均勻地分散。The weight average molecular weight of the graft copolymer is preferably within a range of 1,000 or more and 500,000 or less, more preferably within a range of 3,000 or more and 400,000 or less, and still more preferably within a range of 5,000 or more and 300,000 or less. By being in the said range, the particle|grains, such as a colorant, can be uniformly dispersed.

本發明之實施方式中所使用之上述接枝共聚物亦可除上述通式(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進而具有其他結構單元。例如可如下所述導入其他結構單元,即,適當地選擇能夠與衍生出上述通式(I)所表示之結構單元之乙烯性不飽和單體等進行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 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, another structural unit can be introduced by appropriately selecting an ethylenically unsaturated monomer that can be copolymerized with an ethylenically unsaturated monomer from which the structural unit represented by the general formula (I) is derived, and copolymerization. And import other structural units.

(嵌段共聚物) 關於作為酸性分散劑而較佳之嵌段共聚物,例如可列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,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,提高耐熱性之觀點而言,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)所表示之結構單元只要作為色料親和性部位發揮功能即可,可包含一種結構單元,亦可包含兩種以上之結構單元。於包含兩種以上之結構單元之情形時,在包含上述通式(I)所表示之結構單元之嵌段部內,兩種以上之結構單元可無規地排列。 (block copolymer) The block copolymer that is preferable as an acidic dispersant includes, for example, a block portion containing a structural unit represented by the above general formula (I) and a block containing a structural unit represented by the above general formula (III). part of the block copolymer. In this block copolymer, in the block part containing the structural unit represented by the said general formula (I), it is preferable that the structural unit represented by the said general formula (I) contains 3 or more in total. Among them, from the viewpoint of improving dispersibility and improving heat resistance, it is preferably 3 or more and 200 or less, more preferably 3 or more and 50 or less, still more preferably 3 or more and 30 the following. The structural unit represented by the above-mentioned general formula (I) only needs to function as a colorant-affinity site, and may include one kind of structural unit or two or more kinds of structural units. In the case of including two or more structural units, in the block portion including the structural unit represented by the general formula (I), the two or more structural units may be randomly arranged.

上述嵌段共聚物中,相對於上述嵌段共聚物之所有結構單元,上述通式(I)所表示之結構單元之合計含有比率較佳為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,則嵌段共聚物中之與粒子之親和性部位之比率變得適當,且可抑制對有機溶劑之溶解性之降低,因此對色料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可穩定地局部存在於色料周邊,因此可獲得耐熱性及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) with respect to all the structural units of the above-mentioned block copolymer is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass. The mass % or more is 70 mass % or less, and more preferably 20 mass % or more and 60 mass % or less. Within the above range, the ratio of the affinity site to the particles in the block copolymer becomes appropriate, and the decrease in solubility in organic solvents can be suppressed, so that the adsorption to particles such as colorants 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 locally in the periphery of the colorant, so that a color filter excellent in heat resistance and 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,色料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)之耐受性(耐NMP性)優異。The above-mentioned block copolymer has a block portion containing 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 colorant are good, and the heat resistance is also good, Furthermore, it is excellent in resistance to N-methylpyrrolidone (NMP) (NMP resistance).

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,可選用與上述R 12中所示之烴基相同者。 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 , -[ A valent group represented by CO-(CH 2 ) y2 -O] z2 -R 30 , -CO-OR 30' or -O-CO-R 30 " . As the hydrocarbon group in R 27 , the same as the above-mentioned R 12 can be selected. The hydrocarbon groups shown in are 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。 關於上述R 30中之烴基,可選用與上述R 12中所示之烴基相同者。 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可彼此相同,亦可不同。 Further, the above R 30 is a hydrogen atom, a hydrocarbon group, -CHO, -CH 2 CHO or a valent group represented by -CH 2 COOR 31 , and R 30' is a hydrocarbon group, -[CH(R 28 )-CH(R 29 ) A valent group represented by -O] x2' -R 30 , -[(CH 2 ) y2' -O] z2' -R 30 , -[CO-(CH 2 ) y2' -O] z2' -R 30 , R 30 " is an alkyl group with 1 to 18 carbon atoms, R 31 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and the above-mentioned hydrocarbon group may have a substituent. About the above R 30 The hydrocarbon group may be the same as the hydrocarbon group shown in the above R 12. In the above R 27 and R 30' , x2 and x2' are the same as the above x, y2 and y2' are the same as the above y, z2 and z2' are the same as the above z is the same.In addition, R 27 in the structural unit represented by the general formula (III) may be the same or different from each other.

作為上述R 27及R 30',其中較佳為使用與有機溶劑之溶解性優異者,例如可列舉與上述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可於不妨礙上述嵌段共聚物之分散性能等之範圍內經烷氧基、羥基、羧基、胺基、環氧基、異氰酸基、氫鍵形成基等取代基取代,又,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反應而加成上述取代基。又,亦可於合成具有該等取代基之嵌段共聚物後,使具有與該取代基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,或者使具有異氰酸基之嵌段共聚物與(甲基)丙烯酸羥基乙酯進行反應而加成聚合性基。 Among the above-mentioned R 27 and R 30' , those having excellent solubility in organic solvents are preferably used, and for example, the same ones as those of the above-mentioned R 33 and R 37 can be mentioned. In addition, R 27 , R 30 , R 30 ′ , R 30 " and R 31 in the general formula (IV) can be alkoxy, hydroxyl, carboxyl, Substituents such as amino groups, epoxy groups, isocyanate groups, and hydrogen bond forming groups can be substituted, and the above-mentioned substituents can be added by reacting with a compound having the above-mentioned substituents after synthesizing the above-mentioned block copolymer. In addition, after synthesizing a block copolymer having these substituents, a compound having a functional group reactive with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, a glycidyl group may be added. The block copolymer is reacted with (meth)acrylic acid, or the block copolymer having an isocyanate group is reacted with hydroxyethyl (meth)acrylate to add a polymerizable group.

關於構成包含通式(III)所表示之結構單元之嵌段部之結構單元之數量,並無特別限制,但就溶劑親和性部位與色料親和性部位有效地發揮作用,提高色料分散液之分散性之觀點而言,上述結構單元之數量較佳為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, but the solvent-affinity portion and the colorant-affinity portion effectively function to improve the colorant dispersion. From the viewpoint of dispersibility, the number of the structural units is preferably 10 or more and 200 or less, more preferably 20 or more and 100 or less, and still more preferably 30 or more and 80 or less.

上述嵌段共聚物中,相對於上述嵌段共聚物之所有結構單元,通式(III)所表示之結構單元之含有比率較佳為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, with respect to all the structural units in the above-mentioned block copolymer. More than 90 mass % or less.

關於包含通式(III)所表示之結構單元之嵌段部,只要以作為溶劑親和性部位發揮功能之方式進行選擇即可,通式(III)所表示之結構單元可包含一種結構單元,亦可包含兩種以上之結構單元。本發明之實施方式中,於通式(III)所表示之結構單元包含兩種以上之結構單元之情形時,包含上述通式(III)所表示之結構單元之嵌段部內,兩種以上之結構單元可無規地排列。The block portion including the structural unit represented by the general formula (III) may be selected so as to function as a solvent affinity portion, and the structural unit represented by the general formula (III) may include one kind of structural unit, or Can contain two or more structural units. In the embodiment of the present invention, when the structural unit represented by the general formula (III) includes two or more kinds of structural units, in the block portion of the structural unit represented by the general formula (III), two or more kinds of structural units are included. The structural units can be arranged randomly.

於被用作分散劑之嵌段共聚物中,作為包含通式(I)所表示之結構單元之嵌段部之結構單元之單元數m、與包含通式(III)所表示之結構單元之嵌段部之結構單元之單元數n的比率m/n,較佳為0.01以上1以下之範圍內,就色料之分散性、分散穩定性之觀點而言,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 as the structural unit of the block portion containing the structural unit represented by the general formula (I) and the number m of the structural unit containing the structural unit represented by the general formula (III) The ratio m/n of the unit number n of the structural unit of the block portion is preferably in the range of 0.01 or more and 1 or less, and more preferably 0.1 or more and 0.7 or less from the viewpoints of dispersibility and dispersion stability of the colorant within the range.

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,可使色料穩定地分散即可,並無特別限定,但就與色料之交互作用優異,可有效地抑制分散劑彼此之凝聚之觀點而言,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 sequence of the above-mentioned block copolymer, as long as it has a block portion containing the structural unit represented by the general formula (I) and a block portion containing the structural unit represented by the general formula (III), the colorant can be What is necessary is to disperse stably, and it is not particularly limited, but from the viewpoint of excellent interaction with the colorant, and from the viewpoint of effectively suppressing the aggregation of dispersants, it is preferable to include the structural unit represented by the general formula (I) above. The block portion is only bonded 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,但就使分散性變得良好,耐熱性優異之觀點而言,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 above-mentioned block copolymer is not particularly limited, but from the viewpoint of improving dispersibility and excellent heat resistance, it is preferably 2,500 or more and 500,000 or less, more preferably 3,000 or more and 400,000 or less, still more preferably It is above 6000 and below 300000.

關於具有上述通式(I)所表示之結構單元之聚合物之酸值,就上述色料之分散性及保存穩定性之觀點而言,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,就顯影性優異之觀點而言,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 general formula (I) is preferably 20 mgKOH/g or more, more preferably 30 mgKOH, from the viewpoints of the dispersibility and storage stability of the colorant. /g or more, more preferably 40 mgKOH/g or more. On the other hand, from the viewpoint of being excellent in developability, the acid value of the polymer having the structural unit represented by the 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 the present invention, the acid value refers to the 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.

<其他酸性分散劑> 於本發明之色料分散液中,可進而包含與具有上述通式(I)所表示之結構單元之聚合物不同之其他酸性分散劑。 作為其他酸性分散劑,可列舉具有酸性基之分散劑。此處,作為酸性基,例如可列舉羧基、磺基、或磷酸基等,但作為其他酸性分散劑之分散劑中所含之酸性基,其中就分散性優異之觀點而言,較佳為羧基。 <Other acidic dispersants> In the color material dispersion liquid of the present invention, other acidic dispersants different from the polymer having the structural unit represented by the general formula (I) may be further contained. As another acidic dispersing agent, the dispersing agent which has an acidic group is mentioned. Here, examples of the acidic group include a carboxyl group, a sulfo group, a phosphoric acid group, and the like, but as an acidic group contained in a dispersant of other acidic dispersants, a carboxyl group is preferred from the viewpoint of excellent dispersibility. .

就分散性優異之觀點而言,其他酸性分散劑之酸值較佳為30 mgKOH/g以上250 mgKOH/g以下之範圍內,其中較佳為40 mgKOH/g以上,更佳為50 mgKOH/g以上,進而較佳為70 mgKOH/g以上。另一方面,就抑制顯影殘渣之觀點而言,其他酸性分散劑之酸值較佳為200 mgKOH/g以下,更佳為190 mgKOH/g以下,進而較佳為180 mgKOH/g以下。From the viewpoint of excellent dispersibility, the acid value of other acidic dispersants is preferably in the range of 30 mgKOH/g or more and 250 mgKOH/g or less, preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g. or more, more preferably 70 mgKOH/g or more. On the other hand, from the viewpoint of suppressing development residues, the acid value of other acidic dispersants is preferably 200 mgKOH/g or less, more preferably 190 mgKOH/g or less, and still more preferably 180 mgKOH/g or less.

於本發明中,作為其他酸性分散劑,就藉由與具有上述通式(I)所表示之結構單元之聚合物組合使用而使顯影殘渣之抑制性提高之觀點而言,較佳為具有羧基之高分子分散劑;其中,就藉由與具有上述通式(I)所表示之結構單元之聚合物組合使用而使顯影殘渣之抑制性提高,且使塗膜之均勻性變得更良好之觀點而言,較佳為包含下述A嵌段及下述B嵌段之嵌段共聚物,A嵌段包含源自含羧基之乙烯性不飽和單體之結構單元,B嵌段包含源自(甲基)丙烯酸烷基酯之結構單元。 以下,有時將包含下述A嵌段及下述B嵌段之嵌段共聚物簡稱為「含羧基之嵌段共聚物」,A嵌段包含源自含羧基之乙烯性不飽和單體之結構單元,B嵌段包含源自(甲基)丙烯酸烷基酯之結構單元。該含羧基之嵌段共聚物例如適宜用作二苯并哌喃系染料之金屬色澱色料及顏料之分散劑。 In the present invention, as another acidic dispersant, it is preferable to have a carboxyl group from the viewpoint of improving the inhibitory property of developing residues by using in combination with a polymer having a structural unit represented by the above-mentioned general formula (I). The polymer dispersant; among them, by combining with a polymer having a structural unit represented by the above general formula (I), the inhibition of developing residues is improved, and the uniformity of the coating film becomes better. From a viewpoint, a block copolymer comprising the following A block and the following B block is preferable, the A block comprises a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer, and the B block comprises a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer. Structural unit of alkyl (meth)acrylate. Hereinafter, a block copolymer comprising the following A block and the following B block may be abbreviated as a "carboxyl group-containing block copolymer", and the A block comprises a compound derived from a carboxyl group-containing ethylenically unsaturated monomer. Structural units, the B block contains structural units derived from alkyl (meth)acrylates. The carboxyl group-containing block copolymer is suitable, for example, as a dispersant for metallic lake colorants and pigments of dibenzopyran-based dyes.

(含羧基之嵌段共聚物) {A嵌段} 於含羧基之嵌段共聚物中,A嵌段為包含源自含羧基之乙烯性不飽和單體之結構單元之聚合物嵌段。 作為A嵌段中所使用之含羧基之乙烯性不飽和單體,例如可列舉與含有(甲基)丙烯酸羥烷基酯單元之共聚物中所使用之具有羧基之乙烯性不飽和單體相同者。 於A嵌段中包含兩種以上之結構單元之情形時,A嵌段內中之各結構單元可以無規共聚、嵌段共聚等之任一態樣含有,就均勻性之觀點而言,較佳為以無規共聚之態樣含有。 A嵌段中,相對於A嵌段之所有結構單元,源自含羧基之乙烯性不飽和單體之結構單元較佳為40質量%以上,更佳為70質量%以上,進而更佳為僅由源自含羧基之乙烯性不飽和單體之結構單元所構成之聚合物嵌段。 (block copolymer containing carboxyl group) {A block} In the carboxyl group-containing block copolymer, the A block is a polymer block comprising a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer. As the carboxyl group-containing ethylenically unsaturated monomer used in the A block, for example, the same carboxyl group-containing ethylenically unsaturated monomer as the carboxyl group-containing ethylenically unsaturated monomer used in the copolymer containing a hydroxyalkyl (meth)acrylate unit can be mentioned. By. When two or more structural units are contained in the A block, each structural unit in the A block may be contained in any aspect such as random copolymerization, block copolymerization, etc. Preferably, it is contained in the form of random copolymerization. In the A block, the structural units derived from the carboxyl group-containing ethylenically unsaturated monomer are preferably 40% by mass or more, more preferably 70% by mass or more, and still more preferably only 70% by mass or more relative to all the structural units in the A block A polymer block composed of structural units derived from carboxyl-containing ethylenically unsaturated monomers.

A嵌段可僅由源自含羧基之乙烯性不飽和單體之結構單元所構成,亦可於A嵌段之酸度強於B嵌段之酸度之範圍內包含源自與含羧基之乙烯性不飽和單體不同之乙烯性不飽和單體之結構單元。於A嵌段中包含源自與含羧基之乙烯性不飽和單體不同之乙烯性不飽和單體之結構單元的情形時,相對於A嵌段之所有結構單元,較佳為將其設為60質量%以下,更佳為設為30質量%以下。作為與上述含羧基之乙烯性不飽和單體不同之乙烯性不飽和單體,可列舉下述B嵌段中所使用之結構單元。The A block may be composed only of structural units derived from the carboxyl group-containing ethylenically unsaturated monomer, or may also include ethylenic properties derived from and carboxyl group within the range where the acidity of the A block is stronger than that of the B block. Structural units of ethylenically unsaturated monomers different from unsaturated monomers. When the A block contains a structural unit derived from an ethylenically unsaturated monomer different from the carboxyl group-containing ethylenically unsaturated monomer, it is preferable to set it as all the structural units of the A block. 60 mass % or less, and more preferably 30 mass % or less. As an ethylenically unsaturated monomer different from the said carboxyl group-containing ethylenically unsaturated monomer, the structural unit used for the following B block is mentioned.

就分散性及分散穩定性之觀點而言,A嵌段之含量較佳為相對於嵌段共聚物之所有結構單元為5質量%以上,更佳為10質量%以上,另一方面,較佳為95質量%以下,更佳為40質量%以下。From the viewpoint of dispersibility and dispersion stability, the content of the A block is preferably 5% by mass or more, more preferably 10% by mass or more, based on all the structural units of the block copolymer, and on the other hand, preferably It is 95 mass % or less, More preferably, it is 40 mass % or less.

{B嵌段} 於含羧基之嵌段共聚物中,B嵌段為包含源自(甲基)丙烯酸烷基酯之結構單元之聚合物嵌段。 作為B嵌段中所使用之(甲基)丙烯酸烷基酯單體,可與具有上述通式(IV)所表示之結構單元之聚合物鏈中所使用之(甲基)丙烯酸烷基酯單體相同,使用一種或混合兩種以上而使用。 於B嵌段中,除源自(甲基)丙烯酸烷基酯之結構單元以外,亦可含源自其他乙烯性不飽和單體之結構單元。作為源自其他乙烯性不飽和單體之結構單元,可列舉上述通式(III)所表示之結構單元中與源自(甲基)丙烯酸烷基酯之結構單元不同之結構單元。 {B block} In the carboxyl group-containing block copolymer, the B block is a polymer block containing a structural unit derived from an alkyl (meth)acrylate. As the alkyl (meth)acrylate monomer used in the B block, it can be used with the alkyl (meth)acrylate monomer used in the polymer chain having the structural unit represented by the above general formula (IV). The body is the same, use one kind or a mixture of two or more kinds. In addition to the structural unit derived from the alkyl (meth)acrylate, the structural unit derived from another ethylenically unsaturated monomer may be contained in the B block. As a structural unit derived from another ethylenically unsaturated monomer, the structural unit which differs from the structural unit derived from the alkyl (meth)acrylate among the structural units represented by the said general formula (III) is mentioned.

於B嵌段中包含兩種以上之結構單元之情形時,B嵌段內之各結構單元可以無規共聚、嵌段共聚等之任一態樣含有,就均勻性之觀點而言,較佳為以無規共聚之態樣含有。When two or more structural units are contained in the B block, each structural unit in the B block may be contained in any aspect such as random copolymerization, block copolymerization, etc., and is preferred from the viewpoint of uniformity. It is contained in the form of random copolymerization.

B嵌段較佳為,相對於B嵌段之所有結構單元,源自具有酸性基之乙烯性不飽和單體之結構單元為10質量%以下,更佳為5質量%以下,進而較佳為2質量%以下。於本發明中,B嵌段進而更佳為不包含源自具有酸性基之乙烯性不飽和單體之結構單元之聚合物嵌段。The B block is preferably 10 mass % or less of structural units derived from an ethylenically unsaturated monomer having an acidic group with respect to all the structural units of the B block, more preferably 5 mass % or less, and still more preferably 2 mass % or less. In the present invention, the B block is more preferably a polymer block that does not contain a structural unit derived from an ethylenically unsaturated monomer having an acidic group.

上述含羧基之嵌段共聚物可為AB嵌段共聚物,亦可為BAB嵌段共聚物。關於嵌段共聚物為BAB嵌段共聚物時之2個B嵌段之彼此之含有比率,就分散性之觀點而言,較佳為以質量比計調整為50:50~70:30之範圍內。The carboxyl group-containing block copolymer may be an AB block copolymer or a BAB block copolymer. When the block copolymer is a BAB block copolymer, the content ratio of the two B blocks is preferably adjusted to the range of 50:50 to 70:30 in terms of mass ratio from the viewpoint of dispersibility Inside.

就分散性之觀點而言,上述含羧基之嵌段共聚物之酸值較佳為30 mgKOH/g以上250 mgKOH/g以下之範圍內,較佳為以嵌段共聚物之酸值成為該範圍之方式在A嵌段中包含源自含羧基之乙烯性不飽和單體之結構單元。酸值較佳為50 mgKOH/g以上,更佳為70 mgKOH/g以上。酸值較佳為200 mgKOH/g以下,更佳為150 mgKOH/g以下。From the viewpoint of dispersibility, the acid value of the carboxyl group-containing block copolymer is preferably within a range of not less than 30 mgKOH/g and not more than 250 mgKOH/g, preferably the acid value of the block copolymer. In this way, a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer is included in the A block. The acid value is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more. The acid value is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

就分散性之觀點而言,上述含羧基之嵌段共聚物之重量平均分子量較佳為5,000以上100,000以下。上述含羧基之嵌段共聚物之重量平均分子量更佳為8,000以上,進而較佳為10,000以上,另一方面,更佳為80,000以下,進而較佳為70,000以下。From the viewpoint of dispersibility, the weight average molecular weight of the carboxyl group-containing block copolymer is preferably 5,000 or more and 100,000 or less. The weight average molecular weight of the carboxyl group-containing block copolymer is more preferably 8,000 or more, more preferably 10,000 or more, and on the other hand, 80,000 or less, and still more preferably 70,000 or less.

上述含羧基之嵌段共聚物之分子量分佈較佳為未達2,更佳為未達1.5,進而較佳為未達1.3。再者,於本發明中,分子量分佈係指根據「重量平均分子量(Mw))/(數量平均分子量(Mn)」而求出者。分子量分佈越大,便會包含分子量比所設計之聚合物之分子量越小或越大者,從而呈使色料之分散性變差之趨勢,因此較佳為分子量分佈較小。The molecular weight distribution of the carboxyl group-containing block copolymer is preferably less than 2, more preferably less than 1.5, and further preferably less than 1.3. Furthermore, in the present invention, the molecular weight distribution refers to what is calculated according to "weight average molecular weight (Mw))/(number average molecular weight (Mn)". The larger the molecular weight distribution, the more molecular weight than the designed polymer will be included The smaller or larger the molecular weight, the worse the dispersibility of the colorant, so it is preferable to have a smaller molecular weight distribution.

作為上述含羧基之嵌段共聚物之製造方法,可適當選擇先前公知之嵌段共聚物之製造方法而使用。就容易製造組成均勻之聚合物之觀點而言,較佳為使用活性聚合法,作為活性聚合法,可列舉:使用有機酸觸媒及矽烷基系起始劑之方法(GTP(Group transfer polymerization,基團轉移聚合)法)、使用過渡金屬觸媒之方法(ATRP(Atom transfer radical polymerization,原子轉移自由基聚合)法)、使用硫系可逆鏈轉移劑之方法(RAFT(Reversible addition-fragmentation chain transfer,可逆加成斷裂鏈轉移)法)、使用有機碲化合物之方法(TERP(Living radical polymerization,活性自由基聚合)法)等方法。As the manufacturing method of the said carboxyl group-containing block copolymer, the manufacturing method of the block copolymer known previously can be suitably selected and used. From the viewpoint of easy production of a polymer having a uniform composition, a living polymerization method is preferably used. group transfer polymerization) method), a method using a transition metal catalyst (ATRP (Atom transfer radical polymerization, atom transfer radical polymerization) method), a method using a sulfur-based reversible chain transfer agent (RAFT (Reversible addition-fragmentation chain transfer) , reversible addition and fragmentation chain transfer) method), the method using organic tellurium compounds (TERP (Living radical polymerization, living radical polymerization) method) and other methods.

於色料分散液中,分散劑之含量只要適當調整即可,但就分散性及保存穩定性之觀點而言,相對於色料100質量份,較佳為設為5質量份以上80質量份以下,更佳為設為20質量份以上70質量份以下。In the colorant dispersion liquid, the content of the dispersant may be appropriately adjusted, but from the viewpoint of dispersibility and storage stability, it is preferably 5 parts by mass or more and 80 parts by mass relative to 100 parts by mass of the colorant Below, it is more preferable to set it as 20 mass parts or more and 70 mass parts or less.

[其他成分] 於色料分散液中,只要無損本發明之效果,便可進而視需要調配分散輔助樹脂、其他成分。 作為分散輔助樹脂,例如可列舉鹼可溶性樹脂。由於色料粒子彼此因鹼可溶性樹脂之位阻而不易接觸,故而有時可獲得色料之分散變得穩定,或藉由該分散穩定效果而減少分散劑之量之效果。 又,作為其他成分,例如可列舉:用於提高濡濕性之界面活性劑、用於提高密接性之矽烷偶合劑、消泡劑、防縮孔劑、解凝劑、紫外線吸收劑等。 [other ingredients] In the color material dispersion liquid, as long as the effect of the present invention is not impaired, a dispersing auxiliary resin and other components can be further prepared as necessary. As a dispersion auxiliary resin, an alkali-soluble resin is mentioned, for example. Since the colorant particles are not easily brought into contact with each other due to the steric hindrance of the alkali-soluble resin, the dispersion of the colorant may be stabilized, or the effect of reducing the amount of the dispersant by the dispersion stabilization effect may be obtained. Moreover, as other components, surfactant for improving wettability, silane coupling agent for improving adhesiveness, defoaming agent, anti-cratering agent, decoagulation agent, ultraviolet absorber etc. are mentioned, for example.

[溶劑] 作為色料分散液所含有之溶劑,可使用與上述本發明之感光性著色樹脂組合物所含之溶劑相同者。 相對於色料分散液總量,溶劑之量通常較佳為55質量%以上95質量%以下之範圍內,其中較佳為65質量%以上90質量%以下之範圍內,更佳為70質量%以上88質量%以下之範圍內。若溶劑過少,則黏度上升,而分散性容易降低。又,若溶劑過多,則色料濃度降低,可能難以達成目標色度座標。 [solvent] As the solvent contained in the colorant dispersion liquid, the same solvent as the solvent contained in the photosensitive colored resin composition of the present invention can be used. The amount of the solvent is generally preferably within the range of 55% by mass to 95% by mass, preferably within the range of 65% by mass to 90% by mass, and more preferably within the range of 70% by mass relative to the total amount of the colorant dispersion. Within the range of more than 88% by mass or less. When the amount of the solvent is too small, the viscosity increases and the dispersibility tends to decrease. In addition, when the solvent is too large, the concentration of the colorant decreases, and it may be difficult to achieve the target chromaticity coordinates.

[色料分散液之製造方法] 色料分散液之製造方法只要為可獲得利用分散劑使色料分散於溶劑中所得之色料分散液之方法,便無特別限定。例如可應用下述製造方法,其包括:準備色料之步驟;準備分散劑之步驟;及於溶劑中,在存在上述分散劑之情況下使上述色料分散之步驟。於溶劑中,在存在分散劑之情況下,可使兩種以上之色料共分散,亦可使一種以上之色料分散或共分散後,將兩種以上之色料分散液加以混合。 於色料之分散時,可使用先前公知之分散機而進行。作為分散機之具體例,可列舉:兩輥研磨機、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,所使用之珠直徑較佳為0.03 mm以上3.0 mm以下,更佳為0.05 mm以上2.0 mm以下。 [Manufacturing method of pigment dispersion] The method for producing the color material dispersion liquid is not particularly limited as long as it is a method for obtaining a color material dispersion liquid obtained by dispersing the color material in a solvent with a dispersant. For example, the following production method can be applied, which includes: a step of preparing a colorant; a step of preparing a dispersant; and a step of dispersing the above-mentioned colorant in a solvent in the presence of the above-mentioned dispersant. In the solvent, in the presence of a dispersant, two or more color materials can be co-dispersed, or more than one color material can be dispersed or co-dispersed, and then two or more color material dispersions can be mixed. When dispersing the colorant, a previously known disperser can be used. Specific examples of the dispersing machine include roller mills such as two-roll mills and three-roll mills, ball mills such as ball mills, and vibration ball mills, paint conditioners, continuous disc type bead mills, and bead mills such as continuous ring bead mills. machine. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03 mm or more and 3.0 mm or less, more preferably 0.05 mm or more and 2.0 mm or less.

III.感光性著色樹脂組合物之硬化物 本發明之感光性著色樹脂組合物含有作為光聚合性化合物之單體作為光硬化性成分,因此藉由使本發明之感光性著色樹脂組合物進行光聚合反應,可獲得本發明之硬化物。例如形成本發明之感光性著色樹脂組合物之塗膜,並使該塗膜乾燥後,進行曝光,以及視需要進行顯影,藉此可獲得本發明之硬化物。作為塗膜之形成、曝光、及顯影之方法,例如可採用與下述本發明之彩色濾光片所具備之著色層之形成時所使用之方法相同之方法。 於本發明之感光性著色樹脂組合物之較佳之實施方式中,含有(甲基)丙烯酸羥烷基酯單元之共聚物等黏合劑樹脂亦具有聚合性官能基。此種較佳之實施方式中之本發明之感光性著色樹脂組合物之硬化物係使包含選自由染料及色澱色料所組成之群中之至少一種之色料溶解或分散於下述基質中而成之硬化物,該基質係藉由包含含有(甲基)丙烯酸羥烷基酯單元之共聚物之黏合劑樹脂、及單體之光聚合反應所生成者。 本發明之硬化物係使包含選自由染料及色澱色料所組成之群中之至少一種之色料溶解或分散於含有下述黏合劑樹脂之基質中而成,該黏合劑樹脂包含含有(甲基)丙烯酸羥烷基酯單元之共聚物,因此本發明之硬化物為高亮度,並且平坦性優異,於已顯影之情形時顯影殘渣之產生得到抑制,從而適宜用作彩色濾光片之著色層。 III. Cured product of photosensitive colored resin composition Since the photosensitive colored resin composition of this invention contains the monomer which is a photopolymerizable compound as a photocurable component, the hardened|cured material of this invention can be obtained by carrying out photopolymerization reaction of the photosensitive colored resin composition of this invention. For example, after forming a coating film of the photosensitive colored resin composition of the present invention, drying the coating film, exposing the coating film, and developing the coating film as necessary, the cured product of the present invention can be obtained. 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 adopted. In preferable embodiment of the photosensitive colored resin composition of this invention, binder resin, such as the copolymer containing a hydroxyalkyl (meth)acrylate unit, also has a polymerizable functional group. The hardened product of the photosensitive colored resin composition of the present invention in such a preferred embodiment dissolves or disperses a colorant containing at least one selected from the group consisting of dyes and lake colorants in the following matrix The hardened product is formed by photopolymerization of a binder resin containing a copolymer containing a hydroxyalkyl (meth)acrylate unit, and a monomer. The cured product of the present invention is obtained by dissolving or dispersing a colorant containing at least one selected from the group consisting of dyes and lake colorants in a matrix containing the following binder resin, the binder resin containing ( As a copolymer of hydroxyalkyl meth)acrylate units, the cured product of the present invention has high brightness and excellent flatness, and the generation of development residues is suppressed in the case of development, so it is suitable for use as a color filter. Shading layer.

IV.彩色濾光片 本發明之彩色濾光片至少具備透明基板、及設置於該透明基板上之著色層,且該著色層之至少1個為本發明之感光性著色樹脂組合物之硬化物。 本發明之彩色濾光片之上述著色層之至少一個係利用下述硬化物而形成,該硬化物係使包含選自由染料及色澱色料所組成之群中之至少一種之色料溶解或分散於含有下述黏合劑樹脂之基質中而成者,該黏合劑樹脂包含含有(甲基)丙烯酸羥烷基酯單元之共聚物,因此本發明之彩色濾光片具備為高亮度,並且平坦性優異,顯影殘渣之產生得到抑制之著色層。 IV. Color Filters The color filter of the present invention includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers is a cured product of the photosensitive colored resin composition of the present invention. At least one of the above-mentioned colored layers of the color filter of the present invention is formed by using a cured product that dissolves or dissolves a colorant including at least one selected from the group consisting of dyes and lake colorants. Dispersed in a matrix containing the following binder resin, the binder resin contains a copolymer containing hydroxyalkyl (meth)acrylate units, so the color filter of the present invention has high brightness and is flat A coloring layer with excellent properties and suppressed development residues.

圖1係表示本發明之彩色濾光片之一例之概略剖視圖。圖1所示之本發明之彩色濾光片10具有:透明基板1、遮光部2、以及作為著色層3之紅色著色層3R、綠色著色層3G及藍色著色層3B。 於本發明之彩色濾光片中,著色層通常形成於下述透明基板上之遮光部之開口部,且包含3色以上之著色圖案。於圖3之例中,形成紅色著色層3R、綠色著色層3G、藍色著色層3B,且以規定之順序排列。各個顏色之著色層係按紅色著色層3R、綠色著色層3G、藍色著色層3B之順序形成。 該著色層之排列方式並無特別限定,例如可採用條紋型、馬賽克型、三角型、4像素配置型等一般之排列。又,著色層之寬度、面積等可任意設定。 該著色層之厚度係藉由調整塗佈方法、著色樹脂組合物之固形物成分濃度或黏度等而適當地控制,通常較佳為1 μm以上5 μm以下之範圍。 FIG. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. The color filter 10 of the present invention shown in FIG. 1 includes a transparent substrate 1 , a light shielding portion 2 , and a red coloring layer 3R, a green coloring layer 3G, and a blue coloring layer 3B as the coloring layers 3 . In the color filter of the present invention, the colored layer is usually formed on the opening of the light-shielding portion on the transparent substrate described below, and includes colored patterns of three or more colors. In the example of FIG. 3, the red coloring layer 3R, the green coloring layer 3G, and the blue coloring layer 3B are formed, and are arranged in a predetermined order. The coloring layers of each color are formed in the order of the red coloring layer 3R, the green coloring layer 3G, and the blue coloring layer 3B. The arrangement of the coloring layers is not particularly limited, and for example, a common 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 arbitrarily set. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the colored resin composition, and the like, and is usually preferably in the range of 1 μm or more and 5 μm or less.

各個顏色之著色層可藉由如下所述之步序來形成。首先,使用噴塗法、浸漬塗佈法、棒式塗佈法、輥式塗佈法、旋轉塗佈法等塗佈方法,將感光性著色樹脂組合物塗佈於已預先形成有遮光部之透明基板上而形成濕式塗膜。 繼而,使用加熱板或烘箱等使該濕式塗膜乾燥後,介隔規定圖案之光罩對其進行曝光,使黏合劑樹脂及單體等進行光聚合反應而製成感光性塗膜。作為曝光時所使用之光源,例如可列舉:低壓水銀燈、高壓水銀燈、金屬鹵素燈等之紫外線、電子束等。曝光量係根據所使用之光源或塗膜之厚度等進行適當調整。  又,亦可於曝光後進行加熱處理,以促進聚合反應。加熱條件係根據所使用之著色樹脂組合物中之各成分之調配比率、或塗膜之厚度等進行適當選擇。 The colored layers of the respective colors can be formed by the steps described below. First, using coating methods such as spray coating, dip coating, bar coating, roll coating, spin coating, etc., the photosensitive colored resin composition is coated on a transparent preliminarily formed light-shielding portion. A wet coating film is formed on the substrate. Next, after drying this wet coating film using a hot plate, an oven, etc., it exposes via a photomask of a predetermined pattern, and photopolymerizes a binder resin, a monomer, etc., and sets it as a photosensitive coating film. As a light source used at the time of exposure, an ultraviolet-ray, an electron beam, etc., such as a low-pressure mercury-vapor lamp, a high-pressure mercury-vapor lamp, and a metal halide lamp, are mentioned, for example. The exposure amount is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, heat treatment can also be performed after exposure to promote the polymerization reaction. The heating conditions are appropriately selected according to the mixing ratio of each component in the coloring resin composition used, the thickness of the coating film, and the like.

繼而,使用顯影液進行顯影處理,溶解並去除未曝光部分,藉此以所需圖案形成塗膜。作為顯影液,通常可使用使鹼溶解於水或水溶性溶劑中所得之溶液。於該鹼性溶液中,可適量添加界面活性劑等。又,顯影方法可採用一般之方法。 於顯影處理後,通常進行顯影液之清洗、著色樹脂組合物之硬化塗膜之乾燥,從而形成著色層。再者,亦可於顯影處理後進行加熱處理,以使塗膜充分硬化。作為加熱條件,並無特別限定,可根據塗膜之用途進行適當選擇。 Next, a development process is performed using a developing solution, and the unexposed part is dissolved and removed, whereby a coating film is formed in a desired pattern. As a developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. In the alkaline solution, an appropriate amount of surfactant and the like may be added. In addition, a general method can be used as a developing method. After the development treatment, usually, washing of the developer solution and drying of the cured coating film of the colored resin composition are performed to form a colored layer. Furthermore, heat treatment may be performed after the development treatment so that the coating film can be sufficiently cured. It does not specifically limit as a heating condition, According to the application of a coating film, it can select suitably.

[遮光部] 本發明之彩色濾光片中之遮光部係於基板上呈圖案狀形成者,可與一般之彩色濾光片中被用作遮光部者相同。 作為該遮光部之圖案形狀,並無特別限定,例如可列舉條紋狀、矩陣狀等形狀。遮光部可為藉由濺鍍法、真空蒸鍍法等所形成之鉻等金屬薄膜。或者,遮光部亦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而成之樹脂層。若為含有遮光性粒子之樹脂層,則有如下等方法: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墨水進行圖案化之方法、對感光性抗蝕劑進行熱轉印之方法。 作為遮光部之膜厚,若為金屬薄膜,則設定為0.2 μm以上0.4 μm以下左右,若為使黑色顏料分散或溶解於黏合劑樹脂中而成者,則設定為0.5 μm以上2 μm以下左右。 [shading part] The light-shielding portion in the color filter of the present invention is formed in a pattern on the substrate, and can be the same as the light-shielding portion in a general 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 such as chromium formed by sputtering, vacuum deposition, or the like. Alternatively, the light-shielding portion may be a resin layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments are contained in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as: a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of patterning a photosensitive resist A method of thermal transfer using etchant. The film thickness of the light-shielding portion is set to 0.2 μm or more and about 0.4 μm or less in the case of a metal thin film, and about 0.5 μm or more and 2 μm or less in the case of dispersing or dissolving a black pigment in a binder resin. .

[透明基板] 作為透明基板,只要為對可見光而言透明之基材即可,並無特別限定,可使用一般之彩色濾光片中所使用之透明基板。具體而言,可列舉:石英玻璃、無鹼玻璃、合成石英板等不具有可撓性之透明剛性材料、或者透明樹脂膜、光學用樹脂板、軟性玻璃等具有可撓性或軟性之透明軟性材料。此種用於彩色濾光片之透明基板通常在表面具有極性基。  就本發明之感光性著色樹脂組合物之基板密接性提高之觀點而言,作為透明基板,較佳為石英玻璃、無鹼玻璃、合成石英板等包含二氧化矽之基板。  該透明基板之厚度並無特別限定,可根據彩色濾光片之用途使用例如50 μm以上1 mm以下左右者。  再者,本發明之彩色濾光片亦可除上述透明基板、遮光部及著色層以外,例如還形成有外覆層或透明電極層、以及用於使液晶材料配向之配向膜、或柱狀間隔件等。本發明之彩色濾光片並不限於上述所例示之構成,可適當地選擇一般用於彩色濾光片中之公知之構成而使用。 [Transparent substrate] The transparent substrate is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for a general color filter can be used. Specifically, transparent rigid materials that do not have flexibility, such as quartz glass, alkali-free glass, and synthetic quartz plate, or transparent flexible materials that have flexibility or flexibility, such as transparent resin films, optical resin plates, and flexible glass, can be used. Material. Such transparent substrates for color filters usually have polar groups on the surface. From the viewpoint of improving the substrate adhesion of the photosensitive colored resin composition of the present invention, the transparent substrate is preferably a substrate containing silica such as quartz glass, alkali-free glass, and synthetic quartz plate. The thickness of the transparent substrate is not particularly limited. According to the application of the color filter, for example, a thickness of 50 μm or more and 1 mm or less can be used. Furthermore, the color filter of the present invention may be formed with, for example, an overcoat layer or a transparent electrode layer, an alignment film for aligning the liquid crystal material, or a columnar shape in addition to the above-mentioned transparent substrate, light shielding portion and coloring layer. Spacers etc. The color filter of the present invention is not limited to the above-exemplified structure, and a well-known structure generally used in color filters can be appropriately selected and used.

V.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,例如可列舉液晶顯示裝置、或有機發光顯示裝置等。 V. Display device The display device of the present invention is characterized by having the above-mentioned color filter of the present invention. In the present invention, the structure of the display device is not particularly limited, and can be appropriately selected from previously known display devices, for example, a liquid crystal display device, an organic light-emitting display device, and the like.

[液晶顯示裝置] 本發明之液晶顯示裝置之特徵在於,具有上述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。 圖2係表示本發明之顯示裝置所屬之液晶顯示裝置之一例的概略圖。如圖2所示,本發明之液晶顯示裝置40具有彩色濾光片10、具有TFT(thin-film transistor,薄膜電晶體)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於該圖2所示之構成,可設為一般使用彩色濾光片之液晶顯示裝置所採用之公知之構成。 [Liquid crystal display device] The liquid crystal display device of the present invention is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device to which the display device of the present invention belongs. As shown in FIG. 2 , the liquid crystal display device 40 of the present invention includes a color filter 10 , a counter substrate 20 including a thin-film transistor (TFT) array substrate, etc., and the color filter 10 formed on the above-mentioned color filter 10 . The liquid crystal layer 30 between the above-mentioned opposite substrate 20 . In addition, the liquid crystal display device of the present invention is not limited to the structure shown in FIG. 2, and can be a known structure adopted by a liquid crystal display device using a color filter in general.

作為本發明之液晶顯示裝置之驅動方式,並無特別限定,可採用一般用於液晶顯示裝置之驅動方式。作為此種驅動方式,例如可列舉: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 Vertal Alignment,多疇垂直取向)方式等。於本發明中,可較佳地使用該等中之任一方式。 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進行適當選擇而使用。 作為液晶層之形成方法,可使用一般用作液晶單元之製作方法之方法,例如可列舉真空注入方式或液晶滴下方式等。 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 used. Examples of such a driving method include a TN (Twisted Nematic) method, an IPS (In Plane Switching) method, an OCB (Optically Compensated Bend) method, and an MVA (Multi- domain Vertal Alignment, multi-domain vertical alignment) method, etc. In the present invention, any of these can be preferably used. Moreover, as a counter board|substrate, it can select suitably according to the drive method etc. of the liquid crystal display device of this invention, and can be used. As a formation method of a liquid crystal layer, the method generally used as a manufacturing method of a liquid crystal cell can be used, for example, a vacuum injection method, a liquid crystal dropping method, etc. are mentioned.

[有機發光顯示裝置] 本發明之有機發光顯示裝置之特徵在於具有上述本發明之彩色濾光片、及有機發光體。 圖3係表示本發明之顯示裝置所屬之有機發光顯示裝置之一例的概略圖。如圖3所示,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。於彩色濾光片10、與有機發光體80之間,可具有有機保護層50及無機氧化膜60。 [Organic Light Emitting Display Device] The organic light-emitting display device of the present invention is characterized by having the above-mentioned color filter of the present invention and an organic light-emitting body. FIG. 3 is a schematic diagram showing an example of an organic light-emitting display device to which the display device of the present invention belongs. As shown in FIG. 3 , the organic light-emitting display device 100 of the present invention includes a color filter 10 and an organic light-emitting body 80 . Between the color filter 10 and the organic light-emitting body 80 , an organic protective layer 50 and an inorganic oxide film 60 may be provided.

作為有機發光體80之積層方法,例如可列舉如下等方法:於彩色濾光片上表面,依序形成透明陽極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;或者將形成於另一基板上之有機發光體80貼合於無機氧化膜60上之方法。關於有機發光體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等其他構成,適宜使用公知者。如此製得之有機發光顯示裝置100例如既可應用於被動驅動方式之有機EL顯示器,又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於該圖3所示之構成,可設為一般使用彩色濾光片之有機發光顯示裝置所採用之公知之構成。 實施例 As a method for laminating the organic light-emitting body 80, for example, a method such as forming a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, and an electron injection layer on the upper surface of the color filter in this order 75, and the method of the cathode 76; or the method of attaching the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60. For other structures of the organic light-emitting body 80, such as the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76, known ones are suitably used. The organic light-emitting display device 100 thus obtained can be applied to, for example, both passively driven organic EL displays and actively driven organic EL displays. Furthermore, the organic light emitting display device of the present invention is not limited to the structure shown in FIG. 3 , and can be a well-known structure generally used in organic light emitting display devices using color filters. Example

以下,示出實施例對本發明進行具體說明。並非藉由該等記載內容來限制本發明。 重量平均分子量(Mw)係依據上述本發明之測定方法,藉由GPC(凝膠滲透層析法)以標準聚苯乙烯換算值形式來求出。 酸值及羥值係藉由依據JIS K 0070:1992之方法而求出。 各製造例中所製造之黏合劑樹脂之黏度係藉由以下方式求出,即,於壓力20~30 hPa、溫度80℃之條件下對所獲得之黏合劑樹脂溶液(固形物成分40質量%)進行減壓乾燥,使其濃縮直至固形物成分濃度達到60質量%後,以90℃之熱水浴進行循環加熱,使用B型黏度計而求出上述黏度。 Hereinafter, an Example is shown and this invention is demonstrated concretely. The present invention is not limited by these descriptions. The weight-average molecular weight (Mw) is determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography) in accordance with the above-mentioned measuring method of the present invention. An acid value and a hydroxyl value were calculated|required by the method based on JISK0070:1992. The viscosity of the binder resin produced in each production example was obtained by applying the obtained binder resin solution (solid content 40% by mass) under the conditions of a pressure of 20 to 30 hPa and a temperature of 80°C. ) was dried under reduced pressure and concentrated until the solid content concentration reached 60% by mass, then the cyclic heating was performed in a 90° C. hot water bath, and the viscosity was determined using a Brookfield viscometer.

(合成例1:色澱色料1之合成) (1)中間物1之合成 參照日本專利特開2018-3013號公報中所記載之中間物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 Intermediate 1 Referring to the production method of Intermediate A-2, Intermediate B-1, and Compound 1-3 described in Japanese Patent Laid-Open No. 2018-3013, Intermediate 1 (product 1) represented by the following chemical formula (a) was obtained rate 87%). From the following analysis results, it was confirmed that the obtained compound was the target compound. ・MS(ESI) (m/z): 677(+), bivalent ・Elemental analysis value: CHN measured value (81.81%, 7.31%, 5.85%); theoretical value (81.77%, 7.36%, 5.90%)

[化17] 化學式(a)

Figure 02_image037
[Chem. 17] Chemical formula (a)
Figure 02_image037

(2)色澱色料1之合成 將關東化學公司製造之十二鎢磷酸-n水合物2.59 g(0.76 mmol)加熱溶解至甲醇40 mL、水40 mL之混合液中,加入上述中間物11.6 g(1.19 mmol),並攪拌1小時。過濾取出沈澱物,並用水進行清洗。對所獲得之沈澱物進行減壓乾燥而獲得下述化學式(b)所表示之色澱色料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 Lake Color Material 1 2.59 g (0.76 mmol) of dodeca-tungstophosphoric acid-n-hydrate manufactured by Kanto Chemical Co., Ltd. was heated and dissolved in a mixed solution of 40 mL of methanol and 40 mL of water, and the above-mentioned intermediate 11.6 was added. g (1.19 mmol) and stirred for 1 hour. The precipitate was removed by filtration and washed with water. The obtained precipitate was dried under reduced pressure to obtain a lake color material 1 represented by the following chemical formula (b) (yield 95%). From the following analysis results, it was confirmed that the obtained compound was the target compound.・31P NMR (d-dmso, ppm)δ-15.15 ・MS (MALDI) (m/z): 1355 (M + ), 2879 (MH 2 - ) ・Elemental analysis value: CHN found (35.55%, 3.24%) , 2.61%); theoretical value (35.61%, 3.20%, 2.57%) Fluorescence X-ray analysis: MoW measured ratio (0%, 100%); theoretical value (0%, 100%)

[化18] 化學式(b)

Figure 02_image039
[Chemical 18] Chemical formula (b)
Figure 02_image039

(合成例2:二苯并哌喃系染料1之合成) 向500 ml之四口燒瓶中添加下述化學式(c)所表示之磺基熒烷化合物40.2質量份、甲醇312質量份、2,6-二甲苯胺6.8質量份及N-甲基鄰甲苯胺6.0質量份,回流30小時。將該反應液於60℃下進行過濾而去除不溶解成分後,於減壓下去除溶劑直至反應液達到約70 ml為止,注入至6%鹽酸200質量份中。繼而,加入水600質量份,並於室溫下攪拌30分鐘後,過濾取出濕濾餅。使該濕濾餅懸浮於100質量份之水中,於60℃下攪拌2小時後,再次進行過濾取出,以60℃之熱水進行水洗後,使其乾燥,藉此獲得27.4質量份之下述化學式所表示之二苯并哌喃系染料1。 (Synthesis Example 2: Synthesis of Dibenzopyran-based Dye 1) To a 500 ml four-necked flask were added 40.2 parts by mass of a sulfofluoran compound represented by the following chemical formula (c), 312 parts by mass of methanol, 6.8 parts by mass of 2,6-xylidine, and N-methyl-o-toluidine 6.0 parts by mass, refluxed for 30 hours. After filtering this reaction liquid at 60 degreeC to remove insoluble components, the solvent was removed under reduced pressure until the reaction liquid reached about 70 ml, and poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake was suspended in 100 parts by mass of water, stirred at 60°C for 2 hours, then filtered out again, washed with hot water at 60°C, and dried to obtain 27.4 parts by mass of the following Dibenzopyran-based dye 1 represented by the chemical formula.

[化19] 化學式(c)

Figure 02_image041
[Chem. 19] Chemical formula (c)
Figure 02_image041

[化20] 二苯并哌喃系染料1

Figure 02_image043
[Chem. 20] Dibenzopyran-based dye 1
Figure 02_image043

(合成例3:二苯并哌喃系染料2之合成) 向500 ml之四口燒瓶中添加上述化學式(c)所表示之磺基熒烷化合物18.0質量份、甲醇312質量份、2,6-二甲苯胺5.4質量份及鄰甲苯胺4.8質量份,回流30小時。將該反應液於60℃下進行過濾而去除不溶解成分後,於減壓下去除溶劑直至反應液達到約70 ml為止,注入至6%鹽酸200質量份中。繼而,加入水600質量份,於室溫下攪拌30分鐘後,過濾取出濕濾餅。使該濕濾餅懸浮於100質量份之水中,並於60℃下攪拌2小時後,再次進行過濾取出,以60℃之熱水進行水洗後,使其乾燥,藉此獲得21.9質量份之下述化學式所表示之中間物I-1。 (Synthesis Example 3: Synthesis of Dibenzopyran-based Dye 2) 18.0 parts by mass of the sulfofluoran compound represented by the above chemical formula (c), 312 parts by mass of methanol, 5.4 parts by mass of 2,6-xylidine, and 4.8 parts by mass of o-toluidine were added to a 500 ml four-necked flask, and refluxed. 30 hours. After filtering this reaction liquid at 60 degreeC to remove insoluble components, the solvent was removed under reduced pressure until the reaction liquid reached about 70 ml, and poured into 200 parts by mass of 6% hydrochloric acid. Next, 600 parts by mass of water was added, and after stirring at room temperature for 30 minutes, the wet cake was taken out by filtration. The wet cake was suspended in 100 parts by mass of water, stirred at 60°C for 2 hours, then filtered out again, washed with hot water at 60°C, and dried to obtain 21.9 parts by mass or less. Intermediate I-1 represented by the chemical formula.

[化21] 中間物I-1

Figure 02_image045
[Chem. 21] Intermediate I-1
Figure 02_image045

繼而,將上述中間物I-1 20質量份、1-甲基-2-吡咯啶酮135.3質量份、碳酸鉀7.8質量份及碘甲烷16.2質量份之混合物於80℃下攪拌2小時。反應結束後,將反應溶液放冷至室溫後,將反應溶液滴加至0~10℃之17.5%鹽酸541.2質量份中,並攪拌1小時。然後,過濾取出析出物,使殘渣於60℃下乾燥24小時,藉此獲得結晶20.4質量份。 將所獲得之結晶20質量份及磷醯氯106質量份放入至燒瓶中,以60℃攪拌2小時。將所獲得之反應溶液放冷至室溫,向冰水1500質量份中滴加反應液,並攪拌30分鐘。過濾分離所獲得之結晶,以水200質量份進行清洗,歷時10小時進行乾燥。使該結晶7質量份、三氟甲基磺醯胺1.8質量份溶解至氯仿40質量份中,滴加三乙胺1.55質量份,於室溫下攪拌1小時。然後,向所獲得之反應溶液中加入水100質量份進行水洗,繼而分取有機層。利用硫酸鈉使有機層乾燥而進行精製,進行減壓濃縮而獲得6.8質量份之下述化學式所表示之二苯并哌喃系染料2(產率80%)。 Next, a mixture of 20 parts by mass of the intermediate I-1, 135.3 parts by mass of 1-methyl-2-pyrrolidone, 7.8 parts by mass of potassium carbonate, and 16.2 parts by mass of methyl iodide was stirred at 80° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 541.2 parts by mass of 17.5% hydrochloric acid at 0 to 10°C, followed by stirring for 1 hour. Then, the precipitate was collected by filtration, and the residue was dried at 60° C. for 24 hours to obtain 20.4 parts by mass of crystals. 20 parts by mass of the obtained crystals and 106 parts by mass of phosphonium chloride were put into a flask, and stirred at 60° C. for 2 hours. The obtained reaction solution was left to cool to room temperature, and the reaction solution was added dropwise to 1500 parts by mass of ice water, followed by stirring for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts by mass of water, and dried over 10 hours. 7 parts by mass of the crystals and 1.8 parts by mass of trifluoromethylsulfonamide were dissolved in 40 parts by mass of chloroform, 1.55 parts by mass of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, 100 parts by mass of water was added to the obtained reaction solution, washed with water, and then the organic layer was separated. The organic layer was dried and purified with sodium sulfate, and concentrated under reduced pressure to obtain 6.8 parts by mass of dibenzopyran-based dye 2 represented by the following chemical formula (yield: 80%).

[化22] 二苯并哌喃系染料2

Figure 02_image047
[Chem. 22] Dibenzopyran-based dye 2
Figure 02_image047

(合成例4:二苯并哌喃系金屬色澱色料3之合成) 將酸性紅289 5.0質量份加入至水500 ml中,於80℃下使其溶解而製備染料溶液。將聚氯化鋁(「商品名:Takibaine#1500」多木化學公司製造,Al 2(OH) 5Cl,鹼度83.5質量%,以氧化鋁量計為23.5質量%)3.85質量份加入至水200 ml中,於80℃下進行攪拌而製備聚氯化鋁水溶液。於80℃下將所製備之聚氯化鋁水溶液歷時15分鐘滴加至上述染料溶液,進而於80℃下攪拌1小時。過濾取出所生成之沈澱物,以水進行清洗。使所獲得之濾餅乾燥,而獲得6.30質量份之作為二苯并哌喃系染料之金屬色澱色料之二苯并哌喃系金屬色澱色料3(產率96.2%)。 (Synthesis Example 4: Synthesis of Dibenzopyran-based Metal Lake Color Material 3) 5.0 parts by mass of Acid Red 289 was added to 500 ml of water, and dissolved at 80°C to prepare a dye solution. 3.85 parts by mass of polyaluminum chloride ("trade name: Takibaine #1500" manufactured by Taki Chemical Co., Ltd., Al 2 (OH) 5 Cl, basicity 83.5 mass %, 23.5 mass % in terms of alumina amount) was added to water 200 ml was stirred at 80°C to prepare an aqueous polyaluminum chloride solution. The prepared polyaluminum chloride aqueous solution was added dropwise to the above dye solution at 80°C over 15 minutes, and further stirred at 80°C for 1 hour. The resulting precipitate was collected by filtration and washed with water. The obtained filter cake was dried to obtain 6.30 parts by mass of dibenzopyran-based metallic lake coloring material 3 (yield 96.2%) as a metallic lake coloring material for dibenzopyran-based dyes.

(合成例5:鹼性處理PB15:6之合成) 向反應容器中加入氯磺酸300質量份及酞菁銅30質量份,於完全溶解後,加入亞硫醯氯24質量份,緩慢升溫,於101℃下使之反應3小時。將該反應液注入至冰水9000質量份中,攪拌後進行過濾、水洗。利用水300質量份將所獲得之壓濾餅製成漿料後,加入1,1-二乙基-1,5-二氮雜戊烷13質量份,於65℃下攪拌4小時後,進行過濾、水洗、乾燥而獲得用於表面處理之具有鹼性部位之藍色色料衍生物1。關於所獲得之具有鹼性部位之藍色色料衍生物1,確認到其為下述化學式(d)之結構。 ・TOF-MS:768.35 (Synthesis Example 5: Synthesis of PB15:6 by Alkaline Treatment) 300 parts by mass of chlorosulfonic acid and 30 parts by mass of copper phthalocyanine were added to the reaction container, and after completely dissolving, 24 parts by mass of thionyl chloride was added, the temperature was gradually raised, and the reaction was carried out at 101° C. for 3 hours. The reaction solution was poured into 9000 parts by mass of ice water, and after stirring, filtration and water washing were performed. After slurrying the obtained press cake with 300 parts by mass of water, 13 parts by mass of 1,1-diethyl-1,5-diazapentane was added, and the mixture was stirred at 65° C. for 4 hours. Filter, wash with water, and dry to obtain Blue Color Derivative 1 with Basic Sites for Surface Treatment. The obtained blue colorant derivative 1 having a basic moiety was confirmed to be the structure of the following chemical formula (d). ・TOF-MS: 768.35

[化23]  化學式(d)

Figure 02_image049
[Chem. 23] Chemical formula (d)
Figure 02_image049

利用磨碎機將市售之C.I.顏料藍15:6(ε型酞菁銅顏料,DIC公司製造之FASTOGEN BLUE A510)100質量份、及上述具有鹼性部位之藍色色料衍生物1之5質量份於60℃下歷時1.5小時進行乾式粉碎。對該粉碎產物進而混合上述具有鹼性部位之藍色色料衍生物1之5質量份,藉此獲得作為經鹼性處理之C.I.顏料藍15:6之鹼性處理PB15:6。100 parts by mass of commercially available C.I. Pigment Blue 15:6 (ε-type copper phthalocyanine pigment, FASTOGEN BLUE A510 manufactured by DIC Corporation) and 5 parts by mass of the above-mentioned blue pigment derivative 1 having an alkaline moiety were mixed with a grinder. Parts were dry pulverized at 60°C for 1.5 hours. This pulverized product was further mixed with 5 parts by mass of the above-mentioned blue colorant derivative 1 having an alkaline moiety, thereby obtaining an alkaline-treated PB15:6 which is an alkaline-treated C.I. Pigment Blue 15:6.

(合成例6:酸性分散劑A1(具有上述通式(I)所表示之結構單元之聚合物)之合成) (1)巨單體MM-1之合成 向具備冷凝管、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添加丙二醇單甲醚乙酸酯(簡稱PGMEA)80.0質量份,一面於氮氣氣流下進行攪拌一面加溫至溫度90℃。歷時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,進而反應3小時。繼而,停止氮氣氣流,將該反應溶液冷卻至80℃,加入Karenz MOI(昭和電工公司製造)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之GPC測定之結果為重量平均分子量(Mw)4010、數量平均分子量(Mn)1910、分子量分佈(Mw/Mn)2.10。 (Synthesis example 6: Synthesis of acidic dispersant A1 (polymer having a structural unit represented by the above general formula (I))) (1) Synthesis of giant monomer MM-1 80.0 parts by mass of propylene glycol monomethyl ether acetate (abbreviated as PGMEA) was added to a reactor equipped with a condenser, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and the mixture was heated to the temperature while stirring under a nitrogen stream. 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 mass part of azobisisobutyronitrile (abbreviated as AIBN) was further reacted for 3 hours. Next, the nitrogen gas flow was stopped, the reaction solution was cooled to 80° C., and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 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. part, 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 weight 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 向具備冷凝管、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添加PGMEA 85.0質量份,一面於氮氣氣流下進行攪拌一面加溫至溫度90℃。歷時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,加熱並攪拌3小時後,歷時10分鐘滴加AIBN 0.10質量份、PGMEA 10.0質量份之混合液,進而於當前溫度下熟化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之GPC測定之結果為重量平均分子量(Mw)10570、數量平均分子量(Mn)4370、分子量分佈(Mw/Mn)2.42。 (2) Synthesis of graft copolymer A1 85.0 mass parts of PGMEAs were added to the reactor equipped with the condenser, the funnel for addition, the inlet for nitrogen, the mechanical stirrer, and the digital thermometer, and it heated to the temperature of 90 degreeC, stirring under nitrogen flow. 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 (referred to as GMA), 1.24 parts by mass of n-dodecanethiol, and 25.0 parts by mass of PGMEA were added dropwise over 1.5 hours. The mixed solution of 0.5 parts by mass of AIBN and 0.5 parts by mass of AIBN was heated and stirred for 3 hours, then the 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 then aged at the current temperature for 1 hour to obtain grafts 25.0 mass % solution of copolymer A1. As a result of GPC measurement of the obtained graft copolymer A1, the weight 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)具有上述通式(I)所表示之結構單元之聚合物(酸性分散劑A1)之製造 向具備冷凝管、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添加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,一面於氮氣氣流下進行攪拌一面加溫至溫度90℃。歷時30分鐘滴加上述接枝共聚物A1之100.0質量份,加熱並攪拌2小時,藉此獲得具有上述通式(I)所表示之結構單元之聚合物(酸性分散劑A1)溶液(固形物成分25.0質量%)。所獲得之酸性分散劑A1之GMA與PPA之酯化反應之進行係藉由酸值測定與 1H-NMR測定而確認(確認到源自環氧基之峰消失了)。所獲得之酸性分散劑A1之酸值為98 mgKOH/g。 (3) Manufacture of the polymer (acidic dispersant A1) having the structural unit represented by the general formula (I) PGMEA was added to the reactor equipped with a condenser tube, a funnel for addition, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer 27.80 parts by mass and 9.27 parts by mass of phenylphosphonic acid (product name "PPA" manufactured by Nissan Chemical Co., Ltd.) were heated to a temperature of 90° C. while stirring under nitrogen flow. 100.0 parts by mass of the above graft copolymer A1 was added dropwise over 30 minutes, heated and stirred for 2 hours, thereby obtaining a polymer (acidic dispersant A1) solution (solid matter) having the structural unit represented by the above general formula (I). ingredient 25.0 mass %). The progress of the esterification reaction of GMA and PPA of the obtained acidic dispersant A1 was confirmed by acid value measurement and 1 H-NMR measurement (it was confirmed that the peak derived from the epoxy group disappeared). The acid value of the obtained acidic dispersant A1 was 98 mgKOH/g.

(合成例7:酸性分散劑B1(含有包含源自含羧基之乙烯性不飽和單體之結構單元之A嵌段及包含源自(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號中所記載之實施例1來合成下述三嵌段共聚物,該三嵌段共聚物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。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 7: Acidic dispersant B1 (containing an A block containing a structural unit derived from a carboxyl group-containing ethylenically unsaturated monomer and a B block containing a structural unit derived from an alkyl (meth)acrylate) block copolymer) synthesis) With reference to Example 1 described in International Publication No. 2016/132863, the following triblock copolymer was synthesized, the triblock copolymer having 20 parts by mass of methyl methacrylate (MMA), n-butyl methacrylate (BMA) 40 mass parts of blocks, methacrylic acid (MAA) 20 mass parts, BMA 20 mass parts blocks, and MMA 20 mass parts, BMA 40 mass parts blocks. The weight average molecular weight (Mw) of the obtained block copolymer was 11,000, the molecular weight distribution (Mw/Mn) was 1.50, and the acid value was 130 mgKOH/g.

(合成例8:鹼可溶性樹脂A之合成) 向聚合槽中添加150質量份之PGMEA,於氮氣氛圍下升溫至100℃後,歷時1.5小時連續地滴加甲基丙烯酸(MAA)22質量份、甲基丙烯酸環己酯(CHMA)64質量份、及作為光起始劑之PERBUTYL O(日油股份有限公司製造)6質量份、鏈轉移劑(正十二硫醇)2質量份。然後,保持100℃並繼續反應,於主鏈形成用混合物之滴加結束後之2小時後,添加對甲氧基苯酚0.1質量份作為聚合抑制劑而停止聚合。 繼而,一面吹入空氣,一面添加甲基丙烯酸縮水甘油酯(GMA)14質量份作為含環氧基化合物,升溫至110℃後,添加三乙胺0.8質量份,於110℃下歷時15小時進行加成反應,而獲得鹼可溶性樹脂A溶液(重量平均分子量(Mw)9,000,酸值90 mgKOH/g,固形物成分40質量%)。 (Synthesis Example 8: Synthesis of Alkali-Soluble Resin A) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 100° C. under a nitrogen atmosphere, and then 22 parts by mass of methacrylic acid (MAA) and 64 parts by mass of cyclohexyl methacrylate (CHMA) were continuously added dropwise over 1.5 hours. , and 6 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2 parts by mass of a chain transfer agent (n-dodecanethiol). Then, the reaction was continued while maintaining at 100°C, and 2 hours after the completion of the dropwise addition of the main chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound while blowing in air, and after the temperature was raised to 110° C., 0.8 part by mass of triethylamine was added, and the mixture was carried out at 110° C. for 15 hours. The addition reaction was performed to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value 90 mgKOH/g, solid content 40 mass %).

(合成例9:色澱色料4之合成) (1)K 6(P 2MoW 17O 62)之製備 使NaWO 4・2H 2O(和光純藥工業股份有限公司製造)44.0 g、Na 2MoO 4・2H 2O(關東化學股份有限公司製造)1.90 g溶解至純化水230 g中,使用滴加漏斗向該溶液中邊攪拌邊滴加85%磷酸64.9 g。將所獲得之溶液加熱回流8小時。將反應液冷卻至室溫,加入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,過濾分離沈澱物。於90℃下使所獲得之固體乾燥,藉此獲得29.4 g之K 6(P 2MoW 17O 62)。 (2)色澱色料4之合成 將C.I.鹼性藍7(BB7)(東京化成股份有限公司製造)5.30 g投入至純化水350 ml中,於40℃下進行攪拌而使其溶解,從而製備BB7溶液。與此分開地,使上述(1)中所製備之K 6(P 2MoW 17O 62) 10.0 g溶解至純化水40 ml中。向BB7溶液中投入K 6(P 2MoW 17O 62)溶液,並直接於40℃下攪拌1小時。繼而,使內部溫度上升至80℃,進而攪拌1小時,進行色澱化。冷卻後進行過濾,以300 ml之純化水清洗3次。於90℃下使所獲得之固體乾燥,藉此獲得10.4 g之為黑藍色固體且平均一次粒徑為40 nm之作為三芳基甲烷系染料與聚酸陰離子之色澱色料的色澱色料4。 (Synthesis Example 9: Synthesis of Lake Color Material 4) (1) Preparation of K 6 (P 2 MoW 17 O 62 ) NaWO 4 ·2H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) 44.0 g, Na 2 1.90 g of MoO 4 ·2H 2 O (manufactured by Kanto Chemical Co., Ltd.) was dissolved in 230 g of purified water, and 64.9 g of 85% phosphoric acid was added dropwise to the solution using a dropping funnel while stirring. The obtained solution was heated to reflux for 8 hours. The reaction solution 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 ) were obtained. (2) Synthesis of Lake Color Material 4 5.30 g of CI Basic Blue 7 (BB7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 350 ml of purified water, and stirred and dissolved at 40° C. to prepare BB7 solution. Separately, 10.0 g of K 6 (P 2 MoW 17 O 62 ) prepared in (1) above was dissolved in 40 ml of purified water. The K 6 (P 2 MoW 17 O 62 ) solution was put into the BB7 solution, and the solution was stirred at 40° C. for 1 hour as it was. Then, the internal temperature was raised to 80° C., and the mixture was further stirred for 1 hour to form a lake. After cooling, it was filtered and washed three times with 300 ml of purified water. The obtained solid was dried at 90°C, thereby obtaining 10.4 g of a black-blue solid with an average primary particle size of 40 nm as a lake color of a triarylmethane-based dye and a polyacid anion lake color. Material 4.

(製造例1:黏合劑樹脂1之製造) 向聚合槽中添加150質量份之PGMEA,於氮氣氛圍下升溫至100℃後,歷時1.5小時連續地滴加甲基丙烯酸(MAA)26.9質量份、甲基丙烯酸苄酯(BzMA)38.9質量份、甲基丙烯酸2-羥基乙酯(HEMA)5質量份、及作為光起始劑之PERBUTYL O(日油股份有限公司製造)1.4質量份、鏈轉移劑(正十二硫醇)2.5質量份。然後,保持100℃並繼續反應,於主鏈形成用混合物之滴加結束後之2小時後,添加對甲氧基苯酚0.1質量份作為聚合抑制劑而停止聚合。 繼而,一面吹入空氣,一面添加甲基丙烯酸縮水甘油酯(GMA)29.2質量份作為含環氧基化合物,升溫至110℃後,添加三乙胺0.8質量份,於110℃下歷時15小時進行加成反應,而獲得黏合劑樹脂1溶液(重量平均分子量(Mw)14,900,酸值67 mgKOH/g,羥值129 mgKOH/g,固形物成分40質量%)。 (Production Example 1: Production of Binder Resin 1) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 100° C. under a nitrogen atmosphere, and then 26.9 parts by mass of methacrylic acid (MAA), 38.9 parts by mass of benzyl methacrylate (BzMA), 5 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 1.4 parts by mass of PERBUTYL O (manufactured by NOF Corporation) as a photoinitiator, and 2.5 parts by mass of a chain transfer agent (n-dodecanethiol). Then, the reaction was continued while maintaining at 100°C, and 2 hours after the completion of the dropwise addition of the main chain-forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization. Next, while blowing in air, 29.2 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound, the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the mixture was carried out at 110°C for 15 hours. The addition reaction was performed to obtain a binder resin 1 solution (weight average molecular weight (Mw) 14,900, acid value 67 mgKOH/g, hydroxyl value 129 mgKOH/g, solid content 40 mass %).

(製造例2~9、比較製造例1~9:黏合劑樹脂2~9、比較黏合劑樹脂C1~C9之製造) 於製造例1中,將單體、光起始劑及鏈轉移劑之添加量依據表1進行變更,除此以外,藉由與製造例1相同之方式而獲得製造例2~9之黏合劑樹脂2~9溶液、及比較製造例1~9之比較黏合劑樹脂C1~C9溶液(各黏合劑樹脂溶液為固形物成分40質量%)。 (Production Examples 2 to 9, Comparative Production Examples 1 to 9: Production of Binder Resins 2 to 9 and Comparative Binder Resins C1 to C9) In Production Example 1, the binders of Production Examples 2 to 9 were obtained in the same manner as in Production Example 1, except that the addition amounts of the monomer, photoinitiator and chain transfer agent were changed according to Table 1. The solutions of resins 2 to 9 and the comparative binder resins C1 to C9 solutions of Comparative Production Examples 1 to 9 (each binder resin solution is 40 mass % of solid content).

(比較製造例10:比較黏合劑樹脂C10之製造) 向聚合槽中添加PGMEA 150質量份,於氮氣氛圍下升溫至110℃後,將甲基丙烯酸第三丁基環己酯(t-BuCHMA)81.5質量份、甲基丙烯酸(MAA)15.0質量份、甲基丙烯酸2-羥基乙酯(HEMA)3.5質量份、及作為光起始劑之AIBN 3.0質量份分別歷時1.5小時連續地滴加。然後,保持110℃並攪拌2小時,從而獲得比較黏合劑樹脂C10溶液(固形物成分40質量%)。 (Comparative Production Example 10: Production of Comparative Binder Resin C10) 150 parts by mass of PGMEA was added to the polymerization tank, and the temperature was raised to 110° C. under a nitrogen atmosphere, and then 81.5 parts by mass of tert-butylcyclohexyl methacrylate (t-BuCHMA), 15.0 parts by mass of methacrylic acid (MAA), 3.5 parts by mass of 2-hydroxyethyl methacrylate (HEMA) and 3.0 parts by mass of AIBN as a photoinitiator were continuously added dropwise over 1.5 hours, respectively. Then, it stirred for 2 hours while maintaining 110 degreeC, and obtained the comparative binder resin C10 solution (solid content 40 mass %).

[表1] 表1    黏合劑樹脂 單體(質量份) 光起始劑(質量份) 鏈轉移劑(質量份) 編號 Mw 酸值 (mgKOH/q) 羥值 (mgKOH/q) 樹脂黏度 (mPa・s) HEMA BzMA MAA GMA t-BuCHMA 製造例1 1 14900 67 129 1108 5 38.9 26.9 29.2 - 1.4 2.5 製造例2 2 17500 67 129 2799 5 38.9 26.9 29.2 - 1.4 2.0 製造例3 3 16200 90 114 3826 5 42.1 26.9 26.0 - 1.4 2.0 製造例4 4 18300 86 135 6935 10 37.1 26.9 26.0 - 1.4 2.0 製造例5 5 11000 71 172 794 15 27.9 26.9 30.2 - 1.4 5.0 製造例6 6 13700 70 172 2641 15 27.9 26.9 30.2 - 1.4 3.8 製造例7 7 11500 73 194 926 20 22.9 26.9 30.2 - 1.4 5.5 製造例8 8 12000 110 87 3954 5 49.8 26.9 18.3 - 1.4 2.4 製造例9 9 12000 125 72 5235 5 53.9 26.9 14.2 - 1.4 3.3 比較製造例1 C1 14800 108 79 4090 - 50.9 26.9 22.2 - 1.4 2.0 比較製造例2 C2 12700 124 66 7130 - 54.6 26.9 18.5 - 1.4 2.4 比較製造例3 C3 13700 127 66 8088 - 54.6 26.9 18.5 - 1.4 2.0 比較製造例4 C4 10800 147 36 7570 - 62.0 28.0 10.0 - 1.4 3.3 比較製造例5 C5 10700 76 104 324 - 43.9 26.9 29.2 - 1.4 3.6 比較製造例6 C6 10000 70 129 453 5 38.9 26.9 29.2 - 1.4 3.8 比較製造例7 C7 8300 65 129 238 5 38.9 26.9 29.2 - 1.4 5.5 比較製造例8 C8 8800 73 150 275 10 32.9 26.9 30.2 - 1.4 5.5 比較製造例9 C9 7800 80 166 434 20 34.0 23.6 22.4 - 2.0 6.5 比較製造例10 C10 10000 100 15 343 3.5 - 15.0 - 81.5 3.0 - [Table 1] Table 1 adhesive resin Monomer (parts by mass) Photoinitiator (parts by mass) Chain transfer agent (parts by mass) Numbering Mw Acid value (mgKOH/q) Hydroxyl value (mgKOH/q) Resin viscosity (mPa・s) HEMA BzMA MAA GMA t-BuCHMA Manufacturing Example 1 1 14900 67 129 1108 5 38.9 26.9 29.2 - 1.4 2.5 Manufacturing example 2 2 17500 67 129 2799 5 38.9 26.9 29.2 - 1.4 2.0 Manufacturing Example 3 3 16200 90 114 3826 5 42.1 26.9 26.0 - 1.4 2.0 Manufacturing Example 4 4 18300 86 135 6935 10 37.1 26.9 26.0 - 1.4 2.0 Manufacturing Example 5 5 11000 71 172 794 15 27.9 26.9 30.2 - 1.4 5.0 Manufacturing Example 6 6 13700 70 172 2641 15 27.9 26.9 30.2 - 1.4 3.8 Manufacturing Example 7 7 11500 73 194 926 20 22.9 26.9 30.2 - 1.4 5.5 Manufacturing Example 8 8 12000 110 87 3954 5 49.8 26.9 18.3 - 1.4 2.4 Production Example 9 9 12000 125 72 5235 5 53.9 26.9 14.2 - 1.4 3.3 Comparative Production Example 1 C1 14800 108 79 4090 - 50.9 26.9 22.2 - 1.4 2.0 Comparative Production Example 2 C2 12700 124 66 7130 - 54.6 26.9 18.5 - 1.4 2.4 Comparative Production Example 3 C3 13700 127 66 8088 - 54.6 26.9 18.5 - 1.4 2.0 Comparative Production Example 4 C4 10800 147 36 7570 - 62.0 28.0 10.0 - 1.4 3.3 Comparative Production Example 5 C5 10700 76 104 324 - 43.9 26.9 29.2 - 1.4 3.6 Comparative Production Example 6 C6 10000 70 129 453 5 38.9 26.9 29.2 - 1.4 3.8 Comparative Production Example 7 C7 8300 65 129 238 5 38.9 26.9 29.2 - 1.4 5.5 Comparative Production Example 8 C8 8800 73 150 275 10 32.9 26.9 30.2 - 1.4 5.5 Comparative Production Example 9 C9 7800 80 166 434 20 34.0 23.6 22.4 - 2.0 6.5 Comparative Production Example 10 C10 10000 100 15 343 3.5 - 15.0 - 81.5 3.0 -

(製備例1:色澱色料1分散液之製備) 將合成例1之色澱色料110質量份、合成例6之酸性分散劑A1溶液20質量份(有效固形物成分5.0質量份)、合成例8之鹼可溶性樹脂A溶液7.5質量份(有效固形物成分3.0質量份)、及PGMEA 62.5質量份加以混合,於塗料振盪機(淺田鐵工公司製造)中利用2 mm氧化鋯珠進行1小時預分散,進而利用0.1 mm氧化鋯珠進行4小時正式分散而獲得色澱色料1分散液。 (Preparation Example 1: Preparation of Lake Color Material 1 Dispersion) 110 parts by mass of the lake color material of Synthesis Example 1, 20 parts by mass of the acidic dispersant A1 solution of Synthesis Example 6 (5.0 parts by mass of effective solid content), and 7.5 parts by mass of the solution of alkali-soluble resin A of Synthesis Example 8 (effective solid content) 3.0 parts by mass of the chemical composition) and 62.5 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works) for 1 hour, and further, 0.1 mm zirconia beads were used for 4 hours of pre-dispersion. The dispersion liquid of Lake Color Material 1 was obtained by dispersion.

(製備例2:二苯并哌喃系金屬色澱色料3分散液之製備) 將合成例4之二苯并哌喃系金屬色澱色料3 10質量份、合成例7之酸性分散劑B1溶液16.7質量份(有效固形物成分5.0質量份)、合成例8之鹼可溶性樹脂A溶液7.5質量份(有效固形物成分3.0質量份)、及PGMEA 65.8質量份加以混合,於塗料振盪機(淺田鐵工公司製造)中利用2 mm氧化鋯珠進行1小時預分散,進而利用0.1 mm氧化鋯珠進行4小時正式分散而獲得二苯并哌喃系金屬色澱色料3分散液。 (Preparation Example 2: Preparation of Dibenzopyran-based Metal Lake Color Material 3 Dispersion) 10 parts by mass of dibenzopyran-based metal lake colorant 3 of Synthesis Example 4, 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and alkali-soluble resin of Synthesis Example 8 7.5 parts by mass of solution A (3.0 parts by mass of effective solid content) and 65.8 parts by mass of PGMEA were mixed, and pre-dispersed with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works) for 1 hour, and further 0.1 The mm zirconia beads were formally dispersed for 4 hours to obtain the dibenzopyran-based metal lake color material 3 dispersion liquid.

(製備例3:二苯并哌喃系染料1溶液之製備) 使合成例2之二苯并哌喃系染料1 5.0質量份溶解至二丙酮醇45質量份中而獲得二苯并哌喃系染料1溶液。 (Preparation Example 3: Preparation of Dibenzopyran-based Dye 1 Solution) 5.0 parts by mass of dibenzopyran-based dye 1 of Synthesis Example 2 was dissolved in 45 parts by mass of diacetone alcohol to obtain a solution of dibenzopyran-based dye 1.

(製備例4:二苯并哌喃系染料2溶液之製備) 使合成例3之二苯并哌喃系染料2 5.0質量份溶解至二丙酮醇45質量份中而獲得二苯并哌喃系染料2溶液。 (Preparation Example 4: Preparation of Dibenzopyran-based Dye 2 Solution) 5.0 parts by mass of dibenzopyran-based dye 2 of Synthesis Example 3 was dissolved in 45 parts by mass of diacetone alcohol to obtain a dibenzopyran-based dye 2 solution.

(製備例5:PB15:6分散液之製備) 將合成例5之鹼性處理PB15:6 10質量份、合成例7之酸性分散劑B1溶液16.7質量份(有效固形物成分5.0質量份)、合成例8之鹼可溶性樹脂A溶液7.5質量份(有效固形物成分3.0質量份)、及PGMEA 65.8質量份加以混合,於塗料振盪機(淺田鐵工公司製造)中利用2 mm氧化鋯珠進行1小時預分散,進而利用0.1 mm氧化鋯珠進行6小時正式分散而獲得PB15:6分散液。 (Preparation Example 5: Preparation of PB15:6 Dispersion) Alkaline treatment PB15 of Synthesis Example 5: 6 10 parts by mass, 16.7 parts by mass of the acidic dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and 7.5 parts by mass of the alkali-soluble resin A solution of Synthesis Example 8 ( Effective solid content 3.0 parts by mass) and 65.8 parts by mass of PGMEA were mixed, and pre-dispersed for 1 hour with 2 mm zirconia beads in a paint shaker (manufactured by Asada Iron Works), and further for 6 hours with 0.1 mm zirconia beads. PB15:6 dispersion liquid was obtained by the main dispersion in 15 hours.

(製備例6:PV23分散液之製備) 向30 ml蛋黃醬瓶中放入市售之C.I.顏料紫23(PV23)10重量份、合成例7之酸性分散劑B1溶液16.7質量份(有效固形物成分5.0質量份)、合成例8之鹼可溶性樹脂A溶液7.5質量份(有效固形物成分3.0質量份)、PGMEA 65.8重量份、及直徑2 mm之氧化鋯珠30重量份,於塗料振盪機(淺田鐵鋼公司製造)中進行1小時預壓碎後,再將混合液轉移至另一30 ml蛋黃醬瓶中,加入直徑0.1 mm之氧化鋯珠30重量份,於塗料振盪機中進行5小時振盪而獲得PV23分散液。 (Preparation Example 6: Preparation of PV23 Dispersion) Into a 30 ml mayonnaise bottle were placed 10 parts by weight of commercially available C.I. Pigment Violet 23 (PV23), 16.7 parts by mass of the acid dispersant B1 solution of Synthesis Example 7 (5.0 parts by mass of effective solid content), and the alkali of Synthesis Example 8 7.5 parts by mass of soluble resin A solution (3.0 parts by mass of effective solid content), 65.8 parts by weight of PGMEA, and 30 parts by weight of zirconia beads with a diameter of 2 mm were preliminarily prepared in a paint shaker (manufactured by Asada Steel Co., Ltd.) for 1 hour. After crushing, the mixture was transferred to another 30 ml mayonnaise bottle, 30 parts by weight of zirconia beads with a diameter of 0.1 mm were added, and the mixture was shaken in a paint shaker for 5 hours to obtain a PV23 dispersion.

(製備例7:色澱色料4分散液之製備) 於製備例1中,使用合成例6之色澱色料4 10質量份代替合成例1之色澱色料1 10質量份作為色料,除此以外,藉由與製備例1相同之方式而製備色澱色料4之分散液。 (Preparation Example 7: Preparation of Lake Color Material 4 Dispersion) In Preparation Example 1, 10 parts by mass of the lake color material 4 of Synthesis Example 6 was used instead of 10 parts by mass of the lake color material 1 of Synthesis Example 1 as the color material. A dispersion of Lake Color 4 was prepared.

(製備例I:感光性黏合劑成分1之製備) 相對於製造例1之黏合劑樹脂1溶液(固形物成分40質量%)26.5質量份,添加作為光聚合性化合物之二季戊四醇六丙烯酸酯(DPHA)(ARONIX M402(東亞合成公司製造))24.7質量份、作為光起始劑之Irgacure 907(BASF公司製造,α-胺基酮系光起始劑)3.53質量份、kayacure DETX-S(日本化藥公司製造,9-氧硫𠮿

Figure 110128859-A0304-12-01
系光起始劑,2,4-二乙基9-氧硫𠮿
Figure 110128859-A0304-12-01
)0.39質量份、作為抗氧化劑之IRGANOX1010(BASF公司製造)0.78質量份、PGMEA 44.1質量份而獲得感光性黏合劑成分1。 (Preparation Example I: Preparation of Photosensitive Adhesive Component 1) Dipentaerythritol hexaacrylate ( DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)) 24.7 parts by mass, Irgacure 907 (manufactured by BASF, α-amino ketone-based photoinitiator) as a photoinitiator 3.53 mass parts, kayacure DETX-S (Japan Manufactured by the chemical company, 9-oxysulfur 𠮿
Figure 110128859-A0304-12-01
It is a photoinitiator, 2,4-diethyl 9-oxothiol
Figure 110128859-A0304-12-01
) 0.39 parts by mass, 0.78 parts by mass of IRGANOX1010 (manufactured by BASF Corporation) as antioxidants, and 44.1 parts by mass of PGMEA to obtain photosensitive adhesive component 1.

(製備例II~IX、比較製備例I~X:感光性黏合劑成分2~9、比較感光性黏合劑成分1~10之製備) 於製備例I之感光性黏合劑成分1之製備中,在製備例II~IX中使用製造例2~9之黏合劑樹脂2~9溶液代替製造例1之黏合劑樹脂1溶液,在比較製備例I~X中使用比較製造例C1~C10之比較黏合劑樹脂C1~C10溶液代替製造例1之黏合劑樹脂1溶液,除此以外,藉由與製備例I相同之方式,在製備例II~IX中獲得感光性黏合劑成分2~9,在比較製備例I~X中獲得比較感光性黏合劑成分C1~C10。 (Preparation Examples II to IX, Comparative Preparation Examples I to X: Preparation of Photosensitive Adhesive Components 2 to 9 and Comparative Photosensitive Adhesive Components 1 to 10) In the preparation of the photosensitive adhesive component 1 of the preparation example I, in the preparation examples II to IX, the solutions of the binder resins 2 to 9 of the preparation examples 2 to 9 were used to replace the solution of the binder resin 1 of the preparation example 1. In Examples I to X, the solutions of the comparative binder resins C1 to C10 of the comparative production examples C1 to C10 were used instead of the solution of the binder resin 1 of the production example 1. Photosensitive adhesive components 2 to 9 were obtained in ~IX, and comparative photosensitive adhesive components C1 to C10 were obtained in Comparative Preparation Examples I to X.

(實施例1) 將製備例1之色澱色料1分散液23.2質量份、製備例I之感光性黏合劑成分1 32.1質量份、界面活性劑MEGAFAC R08MH(DIC公司製造)0.03質量份、PGMEA 44.7質量份加以混合而獲得實施例1之感光性著色樹脂組合物。 (Example 1) 23.2 parts by mass of dispersion liquid of Lake Colorant 1 of Preparation Example 1, 32.1 parts by mass of photosensitive adhesive component 1 of Preparation Example 1, 0.03 parts by mass of surfactant MEGAFAC R08MH (manufactured by DIC Corporation), and 44.7 parts by mass of PGMEA were mixed And the photosensitive colored resin composition of Example 1 was obtained.

(實施例2~9、比較例1~10) 於實施例1之感光性著色樹脂組合物之製備中,在實施例2~9中使用感光性黏合劑成分2~9代替感光性黏合劑成分1,在比較例1~10中使用比較感光性黏合劑成分C1~C10代替感光性黏合劑成分1,除此以外,藉由與實施例1相同之方式而獲得實施例2~9及比較例1~10之感光性著色樹脂組合物。 (Examples 2 to 9, Comparative Examples 1 to 10) In the preparation of the photosensitive colored resin composition of Example 1, in Examples 2 to 9, the photosensitive adhesive components 2 to 9 were used instead of the photosensitive adhesive component 1, and in Comparative Examples 1 to 10, the comparative photosensitivity was used. The photosensitive colored resin compositions of Examples 2 to 9 and Comparative Examples 1 to 10 were obtained in the same manner as in Example 1, except that the adhesive components C1 to C10 were used instead of the photosensitive adhesive component 1.

(比較例11~12) 於實施例1之感光性著色樹脂組合物之製備中,以鹼性處理PB15:6與PV23之質量比(鹼性處理PB15:6:PV23)成為86.4:13.6之方式使用PB15:6分散液25.5質量份、及PV23分散液4.0質量份代替色澱色料1分散液23.2質量份,進而在比較例11中使用感光性黏合劑成分2 29.2質量份代替感光性黏合劑成分1 32.1質量份,在比較例12中使用比較感光性黏合劑成分C5 29.2質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為41.3質量份,除此以外,藉由與實施例1相同之方式而獲得比較例11~12之感光性著色樹脂組合物。 (Comparative Examples 11 to 12) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 25.5 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 86.4:13.6 parts by mass, and 4.0 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of lake colorant 1, and in Comparative Example 11, 29.2 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 12, 29.2 parts by mass of the comparative photosensitive binder component C5 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 41.3 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 11 to 12 were obtained.

(實施例10、比較例13~15) 於實施例1之感光性著色樹脂組合物之製備中,以色澱色料1與二苯并哌喃系金屬色澱色料3之質量比(色澱色料1:二苯并哌喃系金屬色澱色料3)成為93.0:7.0之方式使用色澱色料1分散液17.6質量份、及二苯并哌喃系金屬色澱色料3分散液1.32質量份代替色澱色料1分散液23.2質量份,進而在實施例10中使用感光性黏合劑成分2 34.0質量份代替感光性黏合劑成分1 32.1質量份,在比較例13中使用比較感光性黏合劑成分C1 34.0質量份代替感光性黏合劑成分1 32.1質量份,在比較例14中使用比較感光性黏合劑成分C4 34.0質量份代替感光性黏合劑成分1 32.1質量份,在比較例15中使用比較感光性黏合劑成分C6 34.0質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為47.1質量份,除此以外,藉由與實施例1相同之方式而獲得實施例10及比較例13~15之感光性著色樹脂組合物。 (Example 10, Comparative Examples 13 to 15) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake color material 1 and the dibenzopyran-based metal lake color material 3 (lake color material 1: dibenzopyran-based Metal lake color material 3) 17.6 parts by mass of dispersion liquid of lake color material 1 and 1.32 parts by mass of dispersion liquid of dibenzopyran-based metal lake color material 3 are used in place of lake color material 1 so as to be 93.0:7.0 In addition, in Example 10, 34.0 parts by mass of the photosensitive adhesive component 2 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.0 parts by mass of the comparative photosensitive adhesive component C1 was used in Comparative Example 13 instead of the photosensitive adhesive component. 1 32.1 parts by mass of the photosensitive adhesive component, in Comparative Example 14, 34.0 parts by mass of the comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.0 parts by mass of the comparative photosensitive adhesive component C6 was used in the comparative example 15 Example 10 and Comparative Example were obtained in the same manner as in Example 1, except that parts by mass were replaced by 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 47.1 parts by mass The photosensitive coloring resin composition of 13-15.

(實施例11、比較例16~18) 於實施例1之感光性著色樹脂組合物之製備中,以色澱色料1與二苯并哌喃系染料1之質量比(色澱色料1:二苯并哌喃系染料1)成為94.2:5.8之方式使用色澱色料1分散液17.3質量份、及二苯并哌喃系染料1溶液1.06質量份代替色澱色料1分散液23.2質量份,進而在實施例11中使用感光性黏合劑成分2 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例16中使用比較感光性黏合劑成分C1 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例17中使用比較感光性黏合劑成分C4 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例18中使用比較感光性黏合劑成分C6 34.4質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為47.2質量份,除此以外,藉由與實施例1相同之方式而獲得實施例11及比較例16~18之感光性著色樹脂組合物。 (Example 11, Comparative Examples 16 to 18) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the dibenzopyran-based dye 1 (lake colorant 1: dibenzopyran-based dye 1) became 94.2: 17.3 parts by mass of lake color material 1 dispersion liquid and 1.06 mass parts of dibenzopyran-based dye 1 solution were used instead of 23.2 mass parts of lake color material 1 dispersion liquid in Example 11. In Comparative Example 16, 34.4 parts by mass of Comparative Photosensitive Adhesive Component C1 was used instead of 32.1 parts by mass of Photosensitive Adhesive Component 1. In Comparative Example 17 In Comparative Example 18, 34.4 parts by mass of comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of photosensitive adhesive component 1, and 34.4 parts by mass of comparative photosensitive adhesive component C6 was used in place of 32.1 parts by mass of photosensitive adhesive component 1, And except having changed the addition amount of PGMEA from 44.7 mass parts to 47.2 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 11 and Comparative Examples 16-18.

(實施例12、比較例19~21) 於實施例1之感光性著色樹脂組合物之製備中,以色澱色料1與二苯并哌喃系染料2之質量比(色澱色料1:二苯并哌喃系染料2)成為94.2:5.8之方式使用色澱色料1分散液17.3質量份、及二苯并哌喃系染料2溶液1.06質量份代替色澱色料1分散液23.2質量份,進而在實施例12中使用感光性黏合劑成分2 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例19中使用比較感光性黏合劑成分C1 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例20中使用比較感光性黏合劑成分C4 34.4質量份代替感光性黏合劑成分1 32.1質量份,在比較例21中使用比較感光性黏合劑成分C6 34.4質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為47.2質量份,除此以外,藉由與實施例1相同之方式而獲得實施例12及比較例19~21之感光性著色樹脂組合物。 (Example 12, Comparative Examples 19 to 21) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the dibenzopyran-based dye 2 (lake colorant 1: dibenzopyran-based dye 2) became 94.2: 17.3 parts by mass of Lake Colorant 1 Dispersion Liquid and 1.06 parts by mass of Dibenzopyran-based Dye 2 Solution in place of 23.2 parts by mass of Lake Colorant 1 Dispersion Liquid in Example 12 34.4 parts by mass of photosensitive adhesive component 2 instead of 32.1 parts by mass of photosensitive adhesive component 1, in Comparative Example 19, 34.4 parts by mass of comparative photosensitive adhesive component C1 was used instead of 32.1 parts by mass of photosensitive adhesive component 1, in Comparative Example 20 In Comparative Example 21, 34.4 parts by mass of the comparative photosensitive adhesive component C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 34.4 parts by mass of the comparative photosensitive adhesive component C6 was used in place of 32.1 parts by mass of the photosensitive adhesive component 1, And except having changed the addition amount of PGMEA from 44.7 mass parts to 47.2 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 12 and Comparative Examples 19-21.

(比較例22~23) 於實施例1之感光性著色樹脂組合物之製備中,以鹼性處理PB15:6與PV23之質量比(鹼性處理PB15:6:PV23)成為76.5:23.5之方式使用PB15:6分散液17.4質量份、及PV23分散液5.35質量份代替色澱色料1分散液23.2質量份,進而在比較例22中使用感光性黏合劑成分2 32.2質量份代替感光性黏合劑成分1 32.1質量份,在比較例23中使用比較感光性黏合劑成分C5 32.2質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為44.9質量份,除此以外,藉由與實施例1相同之方式而獲得比較例22~23之感光性著色樹脂組合物。 (Comparative Examples 22 to 23) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 17.4 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 76.5:23.5 Parts by mass, and 5.35 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of Lake Colorant 1, and in Comparative Example 22, 32.2 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 23, 32.2 parts by mass of the comparative photosensitive adhesive component C5 was used in place of 32.1 parts by mass of the photosensitive adhesive component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 44.9 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 22 to 23 were obtained.

(實施例13、比較例24~26) 於實施例1之感光性著色樹脂組合物之製備中,以色澱色料1與鹼性處理PB15:6之質量比(色澱色料1:鹼性處理PB15:6)成為59.6:40.4之方式使用色澱色料1分散液18.3質量份、及PB15:6分散液12.4質量份代替色澱色料1分散液23.2質量份,進而在實施例13中使用感光性黏合劑成分2 28.7質量份代替感光性黏合劑成分1 32.1質量份,在比較例24中使用比較感光性黏合劑成分C1 28.7質量份代替感光性黏合劑成分1 32.1質量份,在比較例25中使用比較感光性黏合劑成分C4 28.7質量份代替感光性黏合劑成分1 32.1質量份,在比較例26中使用比較感光性黏合劑成分C6 28.7質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為40.6質量份,除此以外,藉由與實施例1相同之方式而獲得實施例13及比較例24~26之感光性著色樹脂組合物。 (Example 13, Comparative Examples 24 to 26) In the preparation of the photosensitive colored resin composition of Example 1, the mass ratio of the lake colorant 1 and the alkaline treatment PB15:6 (the lake colorant 1: the alkaline treatment PB15:6) was 59.6:40.4. Instead of 23.2 parts by mass of dispersion liquid of lake color material 1, 18.3 parts by mass of dispersion liquid of lake color material 1 and 12.4 parts by mass of dispersion liquid of PB15:6 were used, and 28.7 parts by mass of photosensitive adhesive component 2 were used in Example 13. In place of 1 32.1 parts by mass of the photosensitive binder component, in Comparative Example 24, 28.7 parts by mass of the comparative photosensitive binder component C1 was used in place of 32.1 parts by mass of the photosensitive binder component 1, and in the comparative example 25, the comparative photosensitive binder component was used 28.7 parts by mass of C4 was used instead of 32.1 parts by mass of the photosensitive adhesive component 1, and 28.7 parts by mass of the comparative photosensitive adhesive component C6 was used in Comparative Example 26 instead of 32.1 parts by mass of the photosensitive adhesive component 1, and the addition amount of PGMEA was adjusted from 44.7 Except having changed the mass part to 40.6 mass parts, it carried out similarly to Example 1, and obtained the photosensitive colored resin composition of Example 13 and Comparative Examples 24-26.

(比較例27~28) 於實施例1之感光性著色樹脂組合物之製備中,以鹼性處理PB15:6與PV23之質量比(鹼性處理PB15:6:PV23)成為92.5:7.5之方式使用PB15:6分散液34.8質量份、及PV23分散液2.82質量份代替色澱色料1分散液23.2質量份,進而在比較例27中使用感光性黏合劑成分2 25.6質量份代替感光性黏合劑成分1 32.1質量份,在比較例28中使用比較感光性黏合劑成分C5 25.6質量份代替感光性黏合劑成分1 32.1質量份,且將PGMEA之添加量自44.7質量份變更為36.8質量份,除此以外,藉由與實施例1相同之方式而獲得比較例27~28之感光性著色樹脂組合物。 (Comparative Examples 27 to 28) In the preparation of the photosensitive colored resin composition of Example 1, PB15:6 dispersion liquid 34.8 was used so that the mass ratio of alkali-treated PB15:6 and PV23 (alkaline-treated PB15:6:PV23) became 92.5:7.5 Parts by mass, and 2.82 parts by mass of PV23 dispersion liquid instead of 23.2 parts by mass of dispersion liquid of Lake Colorant 1, and in Comparative Example 27, 25.6 parts by mass of photosensitive adhesive component 2 were used instead of 32.1 parts by mass of photosensitive adhesive component 1, and In Comparative Example 28, 25.6 parts by mass of the comparative photosensitive binder component C5 was used instead of 32.1 parts by mass of the photosensitive binder component 1, and the addition amount of PGMEA was changed from 44.7 parts by mass to 36.8 parts by mass. In the same manner as in Example 1, the photosensitive colored resin compositions of Comparative Examples 27 to 28 were obtained.

(實施例1-2~9-2、比較例1-2~10-2) 於實施例1~9及比較例1~10之感光性著色樹脂組合物之製備中,使用製備例7之色澱色料4分散液代替製備例1之色澱色料1分散液,除此以外,藉由與實施例1~9及比較例1~10相同之方式而獲得實施例1-2~9-2及比較例1-2~10-2之感光性著色樹脂組合物。 (Examples 1-2 to 9-2, Comparative Examples 1-2 to 10-2) In the preparation of the photosensitive colored resin compositions of Examples 1 to 9 and Comparative Examples 1 to 10, the dispersion liquid of Lake Color Material 4 of Preparation Example 7 was used instead of the dispersion liquid of Lake Color Material 1 of Preparation Example 1, except that Other than that, the photosensitive colored resin compositions of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 were obtained in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 10.

[評價方法] <著色層形狀> 將實施例1之感光性著色樹脂組合物以後烘烤後之膜厚成為2.5 μm之方式,使用旋轉塗佈機塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS(股)公司製造,「NA35」)上後,使用加熱板於80℃下進行3分鐘加熱乾燥。然後,介隔用以形成60 μm之線與間距(line & space)之光罩,使用超高壓水銀燈照射60 mJ/cm 2之紫外線,使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液,進行60秒鐘噴淋顯影。然後,於230℃之潔淨烘箱中進行30分鐘後烘烤,藉此製作玻璃基板上以60 μm之線與間距圖案形成有著色層之圖案形成基板。 將各實施例及各比較例之感光性著色樹脂組合物以各自後烘烤後之膜厚成為2.5 μm之方式,使用旋轉塗佈機塗佈於如上所述製作之圖案形成基板上後,使用加熱板於90℃下進行3分鐘加熱乾燥。然後,不介隔光罩而使用超高壓水銀燈照射60 mJ/cm 2之紫外線後,於230℃之潔淨烘箱內進行30分鐘後烘烤,藉此於60 μm之圖案間形成了作為各實施例或各比較例之感光性著色樹脂組合物之硬化膜的著色層。於形成該著色層後,利用KLA-Tencor公司製造之觸針式輪廓儀『P-17』之膜厚計來測定圖案輪廓。以基底圖案之中心作為基準,求出距離中心15 μm之部位與中心部分之膜厚差,根據下述評價基準進行評價。 (著色層形狀評價基準) A:膜厚差未達0.05 μm B:膜厚差為0.05 μm以上且未達0.1 μm C:膜厚差為0.1 μm以上 [Evaluation method] <Shape of colored layer> The photosensitive colored resin composition of Example 1 was coated on a glass substrate with a thickness of 0.7 mm (NH TECHNO GLASS Co., Ltd. product, "NA35") was applied, followed by heating and drying at 80° C. for 3 minutes using a hot plate. Then, using an ultra-high pressure mercury lamp to irradiate ultraviolet rays of 60 mJ/cm 2 through a photomask for forming a line & space of 60 μm, and using a 0.05 mass % potassium hydroxide aqueous solution as an alkaline developer, 60 seconds spray development. Then, post-baking was performed in a clean oven at 230° C. for 30 minutes, thereby producing a pattern-forming substrate in which a coloring layer was formed on a glass substrate with a line and space pattern of 60 μm. The photosensitive colored resin composition of each Example and each Comparative Example was coated on the pattern-forming substrate prepared as described above using a spin coater so that the film thickness after post-baking was 2.5 μm, and then used. The hot plate was heated and dried at 90°C for 3 minutes. Then, after irradiating ultraviolet rays of 60 mJ/cm 2 with an ultra-high pressure mercury lamp without the use of a light shield, post-baking was performed in a clean oven at 230° C. for 30 minutes, thereby forming patterns of 60 μm between the examples as the examples. Or the colored layer of the cured film of the photosensitive colored resin composition of each comparative example. After the colored layer was formed, the pattern profile was measured using a film thickness meter of a stylus profiler "P-17" manufactured by KLA-Tencor Corporation. Using the center of the base pattern as a reference, the difference in film thickness between a portion 15 μm from the center and the center portion was obtained, and the evaluation was performed according to the following evaluation criteria. (Criteria for evaluating the shape of the colored layer) A: The difference in film thickness is less than 0.05 μm B: The difference in film thickness is 0.05 μm or more and less than 0.1 μm C: The difference in film thickness is 0.1 μm or more

<顯影殘渣評價> 將實施例及比較例之感光性著色樹脂組合物分別使用旋轉塗佈機塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS(股)公司製造,「NA35」)上後,使用加熱板於60℃下乾燥3分鐘,藉此形成了厚度2.5 μm之著色層。對於上述形成有著色層之玻璃板,使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液,進行60秒鐘噴淋顯影。目視觀察顯影後之上述著色層之形成部後,利用含有乙醇之拭鏡布(TORAY公司製造,商品名Toraysee MK Clean Cloth)充分地擦拭,目視觀察該拭鏡布之著色程度,根據下述評價基準進行評價。 (顯影殘渣評價基準) A:目視下未確認到顯影殘渣,拭鏡布完全未著色。 B:目視下未確認到顯影殘渣,確認到拭鏡布略微著色。 C:目視下觀察到少許顯影殘渣,確認到拭鏡布之著色。 D:目視下觀察到顯影殘渣,確認到拭鏡布之著色。 <Development Residue Evaluation> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater, respectively, and then coated on a 60-degree heating plate. It was dried at ℃ for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. About the glass plate in which the said coloring layer was formed, using 0.05 mass % potassium hydroxide aqueous solution as an alkaline developing solution, the shower image development was performed for 60 seconds. After the formation of the above-mentioned colored layer after the development was visually observed, it was sufficiently wiped with a lens-wiping cloth containing ethanol (manufactured by TORAY, trade name Toraysee MK Clean Cloth), and the degree of coloration of the lens-wiping cloth was visually observed, and the following evaluation was performed. benchmark for evaluation. (Development Residue Evaluation Criteria) A: No development residue was visually confirmed, and the lens cloth was not colored at all. B: The development residue was not confirmed visually, and the lens wiping cloth was confirmed to be slightly colored. C: A little development residue was observed visually, and the coloring of the lens wiping cloth was confirmed. D: Development residue was observed visually, and coloring of the lens wiping cloth was confirmed.

<亮度> 將實施例及比較例之感光性著色樹脂組合物分別以後烘烤後之色度成為y=0.099之方式,使用旋轉塗佈機塗佈於厚度0.7 mm之玻璃基板(NH TECHNO GLASS(股)製造,「NA35」)上。然後,於80℃之加熱板上進行3分鐘加熱乾燥,不介隔光罩而使用超高壓水銀燈照射60 mJ/cm 2之紫外線,繼而於230℃之潔淨烘箱中進行30分鐘後烘烤,藉此獲得硬化膜(著色膜)。使用奧林巴斯公司製造之「顯微分光測定裝置OSP-SP200」來測定所獲得之著色基板之亮度(Y),根據下述評價基準進行評價。 (亮度評價) A:亮度(Y)為13.0以上 B:亮度(Y)為12.0以上且未達13.0 C:亮度(Y)未達12.0 <Brightness> The photosensitive colored resin compositions of Examples and Comparative Examples were coated on a glass substrate with a thickness of 0.7 mm (NH TECHNO GLASS (NH TECHNO GLASS (NH TECHNO GLASS (NH TECHNO GLASS) stock), "NA35"). Then, it was heated and dried on a heating plate at 80°C for 3 minutes, and an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60 mJ/cm 2 without a light shield, and then baked in a clean oven at 230°C for 30 minutes. This obtains a cured film (colored film). The luminance (Y) of the obtained colored substrate was measured using "microspectroscopy apparatus OSP-SP200" manufactured by Olympus, and evaluated according to the following evaluation criteria. (Brightness evaluation) A: Brightness (Y) is 13.0 or more B: Brightness (Y) is 12.0 or more and less than 13.0 C: Brightness (Y) is less than 12.0

<耐熱性> 藉由與上述亮度之評價相同之方法而獲得硬化膜(著色膜)後,將所獲得之著色膜進而於240℃之潔淨烘箱中進行25分鐘後烘烤,測定該著色膜之色度(L 0、a 0、b 0),然後,進而於240℃之潔淨烘箱中進行50分鐘後烘烤,再次測定所獲得之著色膜之色度(L 1、a 1、b 1)。 藉由下述式,對240℃下之自25分鐘後至75分鐘後這段期間之著色膜之色度變化進行評價。 ΔEab={(L 1-L 0) 2+(a 1-a 0) 2+(b 1-b 0) 2} 1/2ΔEab之值越小,則評價為耐熱性越優異。若為ΔEab未達3.0者,則判斷在實用上無礙。 (耐熱性評價基準) A:ΔEab未達2.0 B:ΔEab為2.0以上且未達3.0 C:ΔEab為3.0以上 <Heat resistance> After obtaining a cured film (colored film) by the same method as the evaluation of the above-mentioned brightness, the obtained colored film was further baked in a clean oven at 240° C. for 25 minutes, and the coloring film was measured. Chromaticity (L 0 , a 0 , b 0 ), then post-baking in a clean oven at 240° C. for 50 minutes, and measuring the chromaticity (L 1 , a 1 , b 1 ) of the obtained colored film again . The chromaticity change of the coloring film in the period from 25 minutes to 75 minutes at 240°C was evaluated by the following formula. ΔEab={(L 1 −L 0 ) 2 +(a 1 −a 0 ) 2 +(b 1 −b 0 ) 2 } 1/2 The smaller the value of ΔEab, the better the heat resistance is evaluated. If ΔEab is less than 3.0, it is judged that there is no problem in practice. (Heat resistance evaluation criteria) A: ΔEab is less than 2.0 B: ΔEab is 2.0 or more and less than 3.0 C: ΔEab is 3.0 or more

於以下之表2~5中,金屬色澱色料3意指合成例4中所獲得之二苯并哌喃系金屬色澱色料3,PB15:6意指合成例5中所獲得之鹼性處理PB15:6,PV23意指市售之C.I.顏料紫23。又,分散劑之A1意指合成例6中所獲得之酸性分散劑A1,分散劑之B1意指合成例7中所獲得之酸性分散劑B1。In the following Tables 2 to 5, metal lake color material 3 means dibenzopyran-based metal lake color material 3 obtained in Synthesis Example 4, and PB15:6 means the base obtained in Synthesis Example 5 Sexual treatment PB15:6, PV23 means commercially available C.I. Pigment Violet 23. In addition, A1 of the dispersant means the acidic dispersant A1 obtained in Synthesis Example 6, and B1 of the dispersant means the acidic dispersant B1 obtained in Synthesis Example 7.

[表2] 表2    感光性黏合劑成分 色料分散液① 色料分散液② 色料質量比(色料①/色料②) PGMEA 評價結果 黏合劑樹脂 質量份 色料 分散劑 質量份 色料 分散劑 質量份 質量份 著色層形狀 顯影殘潼 亮度 耐熱色差ΔEab 實施例1 1 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 B A A A 實施例2 2 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 實施例3 3 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 實施例4 4 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 實施例5 5 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 B A A A 實施例6 6 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 實施例7 7 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 B A A A 實施例8 8 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 實施例9 9 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A A A A 比較例1 C1 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A B A B 比較例2 C2 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A B A B 比較例3 C3 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A B A B 比較例4 C4 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 A C A B 比較例5 C5 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例6 C6 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例7 C7 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例8 C8 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例9 C9 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例10 C10 32.1 色澱色料1 A1 23.2 - - - 100/0 44.7 C A A B 比較例11 2 29.2 PB15:6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A 比較例12 C5 29.2 PB15:6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A [Table 2] Table 2 Photosensitive adhesive ingredients Pigment dispersion ① Pigment dispersion ② Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation results adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape development residue brightness Heat-resistant color difference ΔEab Example 1 1 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 2 2 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 3 3 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 4 4 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 5 5 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 6 6 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 7 7 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 B A A A Example 8 8 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Example 9 9 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A A A A Comparative Example 1 C1 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 2 C2 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 3 C3 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A B A B Comparative Example 4 C4 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 A C A B Comparative Example 5 C5 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 6 C6 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 7 C7 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 8 C8 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 9 C9 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 10 C10 32.1 Lake Color 1 A1 23.2 - - - 100/0 44.7 C A A B Comparative Example 11 2 29.2 PB15: 6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A Comparative Example 12 C5 29.2 PB15: 6 B1 25.5 PV23 B1 4.0 86.4/13.6 41.3 A A C A

[表3] 表3    感光性黏合劑成分 色料分散液① 色料分散液② 色料質量比(色料①/色料②) PGMEA 評價 黏合劑樹脂 質量份 色料 分散劑 質量份 色料 分散劑 質量份 質量份 著色層形狀 顯影殘渣 亮度 實施例10 2 34.0 色澱色料1 A1 17.6 金屬色澱色料3 B1 1.32 93.0/7.0 47.1 A A A 比較例13 C1 34.0 色澱色料1 A1 17.6 金屬色澱色料3 B1 1.32 93.0/7.0 47.1 A B A 比較例14 C4 34.0 色澱色料1 A1 17.6 金屬色澱色料3 B1 1.32 93.0/7.0 47.1 A C A 比較例15 C6 34.0 色澱色料1 A1 17.6 金屬色澱色料3 B1 1.32 93.0/7.0 47.1 C A A 實施例11 2 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料1 - 1.06 94.2/5.8 47.2 A A A 比較例16 C1 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料1 - 1.06 94.2/5.8 47.2 A B A 比較例17 C4 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料1 - 1.06 94.2/5.8 47.2 A C A 比較例18 C6 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料1 - 1.06 94.2/5.8 47.2 C A A 實施例12 2 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料2 - 1.06 94.2/5.8 47.2 A A A 比較例19 C1 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料2 - 1.06 94.2/5.8 47.2 A B A 比較例20 C4 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料2 - 1.06 94.2/5.8 47.2 A C A 比較例21 C6 34.4 色澱色料1 A1 17.3 二苯并哌喃系染料2 - 1.06 94.2/5.8 47.2 C A A 比較例22 2 32.2 PB15:6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C 比較例23 C5 32.2 PB15:6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C [table 3] table 3 Photosensitive adhesive ingredients Pigment dispersion ① Pigment dispersion ② Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Example 10 2 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A A A Comparative Example 13 C1 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A B A Comparative Example 14 C4 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 A C A Comparative Example 15 C6 34.0 Lake Color 1 A1 17.6 Metal Lake Pigment 3 B1 1.32 93.0/7.0 47.1 C A A Example 11 2 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A A A Comparative Example 16 C1 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A B A Comparative Example 17 C4 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 A C A Comparative Example 18 C6 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 1 - 1.06 94.2/5.8 47.2 C A A Example 12 2 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A A A Comparative Example 19 C1 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A B A Comparative Example 20 C4 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 A C A Comparative Example 21 C6 34.4 Lake Color 1 A1 17.3 Dibenzopyran dyes 2 - 1.06 94.2/5.8 47.2 C A A Comparative Example 22 2 32.2 PB15: 6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C Comparative Example 23 C5 32.2 PB15: 6 B1 17.4 PV23 B1 5.35 76.5/23.5 44.9 A A C

[表4] 表4    感光性黏合劑成分 色料分散液① 色料分散液② 色料質量比(色料①/色料②) PGMEA 評價 黏合劑樹脂 質量份 色料 分散劑 質量份 色料 分散劑 質量份 質量份 著色層形狀 顯影殘渣 亮度 實施例13 2 28.7 色澱色料1 A1 18.3 PB15:6 B1 12.4 59.6/40.4 40.6 A A A 比較例24 C1 28.7 色澱色料1 A1 18.3 PB15:6 B1 12.4 59.6/40.4 40.6 A B A 比較例25 C4 28.7 色澱色料1 A1 18.3 PB15:6 B1 12.4 59.6/40.4 40.6 A C A 比較例26 C6 28.7 色澱色料1 A1 18.3 PB15:6 B1 12.4 59.6/40.4 40.6 C A A 比較例27 2 25.6 PB15:6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C 比較例28 C5 25.6 PB15:6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C [Table 4] Table 4 Photosensitive adhesive ingredients Pigment dispersion Pigment dispersion Pigment mass ratio (pigment ①/pigment ②) PGMEA Evaluation adhesive resin parts by mass Pigment Dispersant parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Example 13 2 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A A A Comparative Example 24 C1 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A B A Comparative Example 25 C4 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 A C A Comparative Example 26 C6 28.7 Lake Color 1 A1 18.3 PB15: 6 B1 12.4 59.6/40.4 40.6 C A A Comparative Example 27 2 25.6 PB15: 6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C Comparative Example 28 C5 25.6 PB15: 6 B1 34.8 PV23 B1 2.82 92.5/7.5 36.8 A A C

[表5] 表5    感光性黏合劑成分 色料分散液 PGMEA 評價結果 黏合劑樹脂 質量份 色料 分散劑 質量份 質量份 著色層形狀 顯影殘渣 亮度 耐熱色差ΔEab 實施例1-2 1 32.1 色澱色料4 A1 23.2 44.7 B A B B 實施例2-2 2 32.1 色澱色料4 A1 23.2 44.7 A A B B 實施例3-2 3 32.1 色澱色料4 A1 23.2 44.7 A A B B 實施例4-2 4 32.1 色澱色料4 A1 23.2 44.7 A A B B 實施例5-2 5 32.1 色澱色料4 A1 23.2 44.7 B A B B 實施例6-2 6 32.1 色澱色料4 A1 23.2 44.7 A A B B 實施例7-2 7 32.1 色澱色料4 A1 23.2 44.7 B A B B 實施例8-2 8 32.1 色澱色料4 A1 23.2 44.7 A A B B 實施例9-2 9 32.1 色澱色料4 A1 23.2 44.7 A A B B 比較例1-2 C1 32.1 色澱色料4 A1 23.2 44.7 A B B C 比較例2-2 C2 32.1 色澱色料4 A1 23.2 44.7 A B B C 比較例3-2 C3 32.1 色澱色料4 A1 23.2 44.7 A B B C 比較例4-2 C4 32.1 色澱色料4 A1 23.2 44.7 A C B C 比較例5-2 C5 32.1 色澱色料4 A1 23.2 44.7 C A B C 比較例6-2 C6 32.1 色澱色料4 A1 23.2 44.7 C A B C 比較例7-2 C7 32.1 色澱色料4 A1 23.2 44.7 C A B C 比較例8-2 C8 32.1 色澱色料4 A1 23.2 44.7 C A B C 比較例9-2 C9 32.1 色澱色料4 A1 23.2 44.7 C A B C 比較例10-2 C10 32.1 色澱色料4 A1 23.2 44.7 C A B C [table 5] table 5 Photosensitive adhesive ingredients Pigment dispersion PGMEA Evaluation results adhesive resin parts by mass Pigment Dispersant parts by mass parts by mass Shading layer shape Development residue brightness Heat-resistant color difference ΔEab Example 1-2 1 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 2-2 2 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 3-2 3 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 4-2 4 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 5-2 5 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 6-2 6 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 7-2 7 32.1 Lake Color 4 A1 23.2 44.7 B A B B Example 8-2 8 32.1 Lake Color 4 A1 23.2 44.7 A A B B Example 9-2 9 32.1 Lake Color 4 A1 23.2 44.7 A A B B Comparative Example 1-2 C1 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 2-2 C2 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 3-2 C3 32.1 Lake Color 4 A1 23.2 44.7 A B B C Comparative Example 4-2 C4 32.1 Lake Color 4 A1 23.2 44.7 A C B C Comparative Example 5-2 C5 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 6-2 C6 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 7-2 C7 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 8-2 C8 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 9-2 C9 32.1 Lake Color 4 A1 23.2 44.7 C A B C Comparative Example 10-2 C10 32.1 Lake Color 4 A1 23.2 44.7 C A B C

[結果彙總]  表2~5之結果表明,使用下述實施例1~13及實施例1-2~9-2之感光性著色樹脂組合物所形成之著色層為高亮度,並且平坦性優異,顯影殘渣之產生得到抑制,上述實施例1~13及實施例1-2~9-2之感光性著色樹脂組合物組合含有:包含選自由染料及色澱色料所組成之群中之至少一種之色料、及包含下述共聚物(含有(甲基)丙烯酸羥烷基酯單元之共聚物)之黏合劑樹脂,該共聚物具有包含5~25質量%之通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元之高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g。  又,根據表2中所示之實施例1~9與比較例1~10之比較、及表5中所示之實施例1-2~9-2與比較例1-2~10-2之比較表明,於包含上述通式(1)所表示之色澱色料即色澱色料1、或上述通式(2)所表示之色澱色料即色澱色料4之感光性著色樹脂組合物中,若使用含有(甲基)丙烯酸羥烷基酯單元之共聚物作為黏合劑樹脂,則耐熱性提高。[Results Summary] The results in Tables 2 to 5 show that the colored layers formed using the photosensitive colored resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 have high brightness and are excellent in flatness. , the generation of development residues is suppressed, and the photosensitive coloring resin compositions of Examples 1 to 13 and Examples 1-2 to 9-2 in combination contain: at least one selected from the group consisting of dyes and lake colorants A colorant, and a binder resin comprising the following copolymer (copolymer containing hydroxyalkyl (meth)acrylate units), the copolymer having 5 to 25% by mass represented by the general formula (A) The polymer structure derived from the structural unit of hydroxyalkyl (meth)acrylate, the weight average molecular weight is 11000 or more, and the acid value is 60-130 mgKOH/g. Furthermore, according to the comparison of Examples 1 to 9 and Comparative Examples 1 to 10 shown in Table 2, and the comparison of Examples 1-2 to 9-2 and Comparative Examples 1-2 to 10-2 shown in Table 5 The comparison shows that in the photosensitive colored resin containing the lake color material represented by the above general formula (1), namely the lake color material 1, or the lake color material represented by the above general formula (2), namely the lake color material 4 In the composition, when a copolymer containing a hydroxyalkyl (meth)acrylate unit is used as the binder resin, the heat resistance is improved.

另一方面,於比較例1~4、13~14、16~17、19~20、24~25及1-2~4-2中,使用了不含(甲基)丙烯酸羥烷基酯單元之比較黏合劑樹脂C1~C4之任一者,因此顯影殘渣之抑制效果欠佳。其中,使用了不含(甲基)丙烯酸羥烷基酯單元,重量平均分子量未達11000,且酸值超過130 mgKOH/g之比較黏合劑樹脂C4之比較例4、14、17、20、25及4-2,其顯影殘渣之抑制效果尤其差。  再者,於比較例1~4、13~14、16~17、19~20、24~25及1-2~4-2中,儘管用作黏合劑樹脂之共聚物不含有(甲基)丙烯酸羥烷基酯單元,但著色層之平坦性亦優異,認為其原因在於共聚物之酸值相對較高,為108~147 mgKOH/g。另一方面,於本發明之感光性著色樹脂組合物中,用作黏合劑樹脂之含有(甲基)丙烯酸羥烷基酯單元之共聚物以上述特定量包含(甲基)丙烯酸羥烷基酯單元,藉此,若酸值處於60~130 mgKOH/g之範圍內,則即便酸值相對較高,亦可抑制顯影殘渣之產生。例如,實施例8、9中,所使用之黏合劑樹脂8、9之酸值雖與比較例1~3同等高,但顯影殘渣之產生得到抑制。於本發明之感光性著色樹脂組合物中,用作黏合劑樹脂之含有(甲基)丙烯酸羥烷基酯單元之共聚物以上述特定量包含(甲基)丙烯酸羥烷基酯單元,藉此樹脂組合物中之除黏合劑樹脂以外之顯影性較低之成分與(甲基)丙烯酸羥烷基酯單元進行交互作用,連帶著顯影性較低之成分一起顯影,因此認為可抑制殘渣之產生。於黏合劑樹脂未充分包含(甲基)丙烯酸羥烷基酯單元,而具有較高之酸值之情形時,黏合劑樹脂單一成分時之顯影性會變得過高,而遺棄顯影性較低之成分,因此認為容易產生殘渣。於使用比較黏合劑樹脂C1~C3之比較例中,不含(甲基)丙烯酸羥烷基酯單元,因此顯影殘渣之產生容易受酸值之影響,故認為於酸值為108 mgKOH/g以上時產生了顯影殘渣。On the other hand, in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, those containing no hydroxyalkyl (meth)acrylate units were used In comparison with any one of the binder resins C1 to C4, the effect of suppressing the development residue is not good. Among them, Comparative Examples 4, 14, 17, 20, and 25 of Comparative Examples 4, 14, 17, 20, and 25 of Comparative Binder Resin C4 that did not contain hydroxyalkyl (meth)acrylate units, had a weight-average molecular weight of less than 11,000, and had an acid value of more than 130 mgKOH/g were used. And 4-2, the inhibitory effect of the development residue is particularly poor. Furthermore, in Comparative Examples 1 to 4, 13 to 14, 16 to 17, 19 to 20, 24 to 25, and 1-2 to 4-2, although the copolymers used as binder resins did not contain (methyl) Although the hydroxyalkyl acrylate unit is excellent in the flatness of the colored layer, the reason is considered that the acid value of the copolymer is relatively high, ranging from 108 to 147 mgKOH/g. On the other hand, in the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as a binder resin contains a hydroxyalkyl (meth)acrylate in the above-mentioned specific amount Therefore, if the acid value is in the range of 60 to 130 mgKOH/g, even if the acid value is relatively high, the generation of development residues can be suppressed. For example, in Examples 8 and 9, although the acid values of the binder resins 8 and 9 used were as high as those of Comparative Examples 1 to 3, the generation of development residues was suppressed. In the photosensitive colored resin composition of the present invention, the copolymer containing a hydroxyalkyl (meth)acrylate unit used as a binder resin contains a hydroxyalkyl (meth)acrylate unit in the above-mentioned specific amount, whereby In the resin composition, the components with low developability other than the binder resin interact with the hydroxyalkyl (meth)acrylate unit and develop together with the components with low developability, so it is considered that the generation of residues can be suppressed. . In the case where the binder resin does not contain enough hydroxyalkyl (meth)acrylate units and has a high acid value, the developability of the binder resin as a single component will become too high, and the discard developability will be low Therefore, it is considered that residues are likely to be generated. In the comparative examples using the comparative binder resins C1 to C3, there is no hydroxyalkyl (meth)acrylate unit, so the generation of the development residue is easily affected by the acid value, so it is considered that the acid value is 108 mgKOH/g or more. developed residues.

於比較例5及5-2中使用了不含(甲基)丙烯酸羥烷基酯單元,且重量平均分子量未達11000之比較黏合劑樹脂C5,於比較例6~10、15、18、21、26及6-2~10-2中使用了重量平均分子量未達11000之比較黏合劑樹脂C6~C10,因此分別在著色層之平坦性方面欠佳。 於比較例11~12、22~23及27~28中僅使用顏料作為色料,因此著色層之亮度欠佳。再者,於比較例12、23及28中雖使用了與比較例5相同之比較黏合劑樹脂C5,但著色層之平坦性優異。據此可明確,於使用顏料作為色料之情形時,不易產生著色層之平坦性受損之問題。 In Comparative Examples 5 and 5-2, the comparative adhesive resin C5 which does not contain a hydroxyalkyl (meth)acrylate unit and has a weight average molecular weight of less than 11,000 was used. , 26, and 6-2 to 10-2 used comparative binder resins C6 to C10 with a weight average molecular weight of less than 11,000, so they were inferior in the flatness of the colored layer, respectively. In Comparative Examples 11 to 12, 22 to 23, and 27 to 28, only the pigment was used as the colorant, so the brightness of the colored layer was poor. In addition, in Comparative Examples 12, 23 and 28, although the same comparative adhesive resin C5 as that of Comparative Example 5 was used, the flatness of the colored layer was excellent. From this, it is clear that when a pigment is used as a colorant, the problem that the flatness of the colored layer is not easily damaged.

1:基板 2:遮光部 3:著色層 3B:藍色著色層 3B':藍色塗膜 3G:綠色著色層 3R:紅色著色層 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 3B: blue tinting layer 3B': blue coating 3G: Green Shading Layer 3R: red tinting layer 10: Color filter 20: Opposite 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: Light-emitting layer 75: Electron injection layer 76: Cathode 80: organic light emitters 100: Organic Light Emitting Display Device

圖1係表示本發明之彩色濾光片之一例之概略圖。  圖2係表示本發明之液晶顯示裝置之一例之概略圖。  圖3係表示本發明之有機發光顯示裝置之一例之概略圖。  圖4(a)、圖4(b)、圖4(c)係表示使用含有顏料之感光性著色樹脂組合物來形成彩色濾光片之著色層之習知方法之一例的概略圖。  圖5(a)、圖5(b)、圖5(c)係表示使用含有染料或色澱色料之感光性著色樹脂組合物來形成彩色濾光片之著色層之習知方法之一例的概略圖。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 the liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. 4(a), 4(b), and 4(c) are schematic diagrams showing an example of a conventional method of forming a colored layer of a color filter using a photosensitive colored resin composition containing a pigment. 5(a), 5(b), and 5(c) show an example of a conventional method of forming a coloring layer of a color filter using a photosensitive coloring resin composition containing a dye or lake coloring material. Sketch map.

Figure 110128859-A0101-11-0003-4
Figure 110128859-A0101-11-0003-4

Claims (9)

一種彩色濾光片用感光性著色樹脂組合物,其含有色料、黏合劑樹脂、單體、光起始劑、及溶劑,且  上述色料包含選自由染料及色澱色料所組成之群中之至少一種,  上述黏合劑樹脂包含下述共聚物,該共聚物具有包含5~25質量%之下述通式(A)所表示之源自(甲基)丙烯酸羥烷基酯之結構單元的高分子結構,且重量平均分子量為11000以上,酸值為60~130 mgKOH/g, [化1]  通式(A)
Figure 03_image051
(通式(A)中,R A表示甲基或氫原子,R B表示碳數1~4之伸烷基)。
A photosensitive colored resin composition for a color filter, which contains a colorant, a binder resin, a monomer, a photoinitiator, and a solvent, and the colorant comprises a group selected from the group consisting of dyes and lake colorants At least one of the above-mentioned binder resins includes a copolymer containing 5 to 25% by mass of a structural unit derived from a hydroxyalkyl (meth)acrylate represented by the following general formula (A) It has a high molecular structure with a weight average molecular weight of 11,000 or more, an acid value of 60 to 130 mgKOH/g, and the general formula (A)
Figure 03_image051
(In the general formula (A), RA represents a methyl group or a hydrogen atom, and RB represents an alkylene group having 1 to 4 carbon atoms).
如請求項1之彩色濾光片用感光性著色樹脂組合物,其中上述色料包含色澱色料。The photosensitive colored resin composition for color filters according to claim 1, wherein the colorant comprises a lake colorant. 如請求項1或2之彩色濾光片用感光性著色樹脂組合物,其中上述色料包含下述通式(1)或通式(2)所表示之色澱色料,  [化2]  通式(1)
Figure 03_image053
(通式(1)中,A為與N直接鍵結之碳原子不具有π鍵之a價有機基,該有機基表示至少在與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,於碳鏈中可包含雜原子;B c-表示c價聚酸陰離子;R i~R v分別獨立地表示氫原子、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分別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可分別相同,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;e為0或1,於e為0時不存在鍵;f及g表示0以上4以下之整數,f+e及g+e為0以上4以下;存在複數個之e、f及g可分別相同,亦可不同)  [化3]  通式(2)
Figure 03_image055
(通式(2)中,R I~R VI分別獨立地表示氫原子、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分別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可分別相同,亦可不同;E m-表示m價聚酸陰離子;  m表示2以上之整數;j為0或1,於j為0時不存在鍵;k及l表示0以上4以下之整數,k+j及l+j為0以上4以下;存在複數個之j、k及l可分別相同,亦可不同)。
The photosensitive colored resin composition for color filters according to claim 1 or 2, wherein the colorant comprises a lake colorant represented by the following general formula (1) or general formula (2), Formula 1)
Figure 03_image053
(In the general formula (1), A is an a-valent organic group that does not have a π bond to a carbon atom directly bonded to N, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N , or an aromatic group having the aliphatic hydrocarbon group, which may contain heteroatoms in the carbon chain; B c- represents a c-valent polyacid anion; R i to R v independently represent a hydrogen atom, an alkyl group that may have a substituent Or an aryl group that may have a substituent, R ii and R iii , R iv and R v can be bonded to form a ring structure; R vi and R vii independently represent an alkyl group that may have a substituent group, and a group that may have a substituent group. An alkoxy group, a halogen atom or a cyano group; Ar 1 represents a divalent aromatic group which may have a substituent; R i to R vii and Ar 1 present in plural may be the same or different respectively; a and c represent 2 or more b and d represent integers greater than or equal to 1; e is 0 or 1, and no bond exists when e is 0; f and g represent integers greater than 0 and less than 4, and f+e and g+e are greater than or equal to 0 and less than 4; e, f and g may be the same or different respectively) [Chemical 3] General formula (2)
Figure 03_image055
(In the general formula (2), R I to R VI each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, R I and R II , R III and R IV , R V It can be bonded with R VI to form a ring structure; R VII and R VIII 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; Ar 2 represents a substituent which may have a substituent The divalent aromatic heterocyclic group, there are plural R I to R VIII and Ar 2 which may be the same or different; E m- represents an m-valent polyacid anion; m represents an integer of 2 or more; j is 0 or 1. When j is 0, there is no bond; k and l represent integers between 0 and 4, and k+j and l+j are 0 or more and 4 or less; there are plural j, k and l which may be the same or different respectively).
如請求項3之彩色濾光片用感光性著色樹脂組合物,其中上述色料進而包含選自由二苯并哌喃系染料、與上述通式(1)或通式(2)所表示之色澱色料不同之二苯并哌喃系染料之色澱色料、及C.I.顏料藍15:6所組成之群中之至少一種。The photosensitive colored resin composition for a color filter according to claim 3, wherein the colorant further comprises a color selected from the group consisting of dibenzopyran-based dyes, and a color represented by the general formula (1) or the general formula (2). At least one of the lake color material of dibenzopyran-based dyes with different lake color materials and the group consisting of C.I. Pigment Blue 15:6. 如請求項4之彩色濾光片用感光性著色樹脂組合物,其中上述二苯并哌喃系染料為下述通式(3)或通式(4)所表示之二苯并哌喃系染料,  上述二苯并哌喃系染料之色澱色料為下述通式(5)所表示之二苯并哌喃系染料之金屬色澱色料,  [化4]  通式(3)
Figure 03_image057
(通式(3)中,R 1及R 2分別獨立地為烷基或芳基,R 3及R 4分別獨立地為芳基或雜芳基)  [化5]  通式(4)
Figure 03_image059
(通式(4)中,R 5及R 6分別獨立地為可具有取代基之脂肪族烴基或芳香族烴基,R 7及R 8分別獨立地為可具有取代基之芳香族烴基或芳香族雜環基,且R 7及R 8之至少1個芳香族烴基或芳香族雜環基經脂肪族烴基取代,R 7及R 8彼此不同;L 1及L 2分別獨立地為直接鍵、-SO 2-、或-CO-,R 9為鹵化脂肪族烴基)  [化6]  通式(5)
Figure 03_image061
(通式(5)中,R 1'、R 2'、R 3'及R 4'分別獨立地表示氫原子、烷基、芳基、或雜芳基,R 1 '與R 3 '、R 2'與R 4'可分別鍵結而形成環結構,R 1'與二苯并哌喃環之5位碳原子、R 3'與二苯并哌喃環之7位碳原子、R 2'與二苯并哌喃環之4位碳原子、或R 4'與二苯并哌喃環之2位碳原子可分別鍵結而形成環結構;上述芳基或雜芳基所具有之氫原子可經酸性基或其鹽、或者鹵素原子取代;R 5'表示酸性基或其鹽,x為0~5之整數;其中,通式(5)具有至少2個酸性基或其鹽,且其中1個形成內鹽)。
The photosensitive colored resin composition for color filters according to claim 4, wherein the dibenzopyran-based dye is a dibenzopyran-based dye represented by the following general formula (3) or general formula (4) , the lake color material of the above-mentioned dibenzopyran series dye is the metal lake color material of the dibenzopyran series dye represented by the following general formula (5), [Chem. 4] general formula (3)
Figure 03_image057
(In the general formula (3), R 1 and R 2 are each independently an alkyl group or an aryl group, and R 3 and R 4 are each independently an aryl group or a heteroaryl group) [Chem. 5] General formula (4)
Figure 03_image059
(In the general formula (4), R 5 and R 6 are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent, and R 7 and R 8 are each independently an aromatic hydrocarbon group or an aromatic hydrocarbon group that may have a substituent group. Heterocyclic group, and at least one aromatic hydrocarbon group or aromatic heterocyclic group of R 7 and R 8 is substituted by an aliphatic hydrocarbon group, R 7 and R 8 are different from each other; L 1 and L 2 are independently a direct bond, - SO 2 -, or -CO-, R 9 is a halogenated aliphatic hydrocarbon group) [Chem. 6] General formula (5)
Figure 03_image061
(In general formula (5), R 1' , R 2' , R 3' and R 4' each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, R 1 ' and R 3 ' , R 2' and R 4' can be bonded respectively to form a ring structure, R 1' and the 5th carbon atom of the dibenzopyran ring, R 3' and the 7th carbon atom of the dibenzopyran ring, R 2' The 4-position carbon atom of the dibenzopyran ring, or R 4' and the 2-position carbon atom of the dibenzopyran ring can be respectively bonded to form a ring structure; the hydrogen atom possessed by the above-mentioned aryl or heteroaryl group may be substituted by an acidic group or a salt thereof, or a halogen atom; R 5' represents an acidic group or a salt thereof, and x is an integer of 0 to 5; wherein, the general formula (5) has at least 2 acidic groups or a salt thereof, and wherein 1 forms the inner salt).
如請求項1或2之彩色濾光片用感光性著色樹脂組合物,其進而含有分散劑。The photosensitive colored resin composition for color filters according to claim 1 or 2, which further contains a dispersant. 一種硬化物,其係如請求項1至6中任一項之彩色濾光片用感光性著色樹脂組合物之硬化物。A hardened product, which is a hardened product of the photosensitive colored resin composition for color filters according to any one of claims 1 to 6. 一種彩色濾光片,其至少具備基板、及設置於該基板上之著色層,且該著色層之至少1個為如請求項1至6中任一項之彩色濾光片用感光性著色樹脂組合物之硬化物。A color filter comprising at least a substrate and a colored layer disposed on the substrate, and at least one of the colored layers is a photosensitive colored resin for a color filter according to any one of claims 1 to 6 Hardened product of the composition. 一種顯示裝置,其具有如請求項8之彩色濾光片。A display device having a color filter as claimed in claim 8.
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