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TWI729272B - Color material dispersion liquid for color filter, dispersant, photosensitive color resin composition for color filter, color filter, and display device - Google Patents

Color material dispersion liquid for color filter, dispersant, photosensitive color resin composition for color filter, color filter, and display device Download PDF

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TWI729272B
TWI729272B TW107106607A TW107106607A TWI729272B TW I729272 B TWI729272 B TW I729272B TW 107106607 A TW107106607 A TW 107106607A TW 107106607 A TW107106607 A TW 107106607A TW I729272 B TWI729272 B TW I729272B
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TW201841960A (en
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大島裕史
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日商Dnp精細化工股份有限公司
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • GPHYSICS
    • 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

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Abstract

Provided is a color material dispersion liquid for a color filter, comprising a color material, a dispersant and a solvent, wherein the dispersant is a block copolymer comprising a block A including a constitutional unit represented by the following general formula (I) and a block B including at least one selected from a constitutional unit represented by the following general formula (B1) and a constitutional unit represented by the following general formula (B2): (the symbols in the general formulae (I), (B1) and (B2) are as described in the specification.)

Description

彩色濾光片用色材分散液、分散劑、彩色濾光片用感光性著色樹脂組成物、彩色濾光片、顯示裝置 Color material dispersion liquid for color filter, dispersant, photosensitive colored resin composition for color filter, color filter, display device

本發明係關於一種彩色濾光片用色材分散液、分散劑、彩色濾光片用感光性著色樹脂組成物、彩色濾光片、及顯示裝置。 The present invention relates to a color material dispersion liquid for color filters, a dispersant, a photosensitive colored resin composition for color filters, a color filter, and a display device.

近年來,隨著個人電腦之發展、尤其是可攜式個人電腦之發展,液晶顯示器之需求增加。移動式顯示器(行動電話、智慧型手機、平板個人電腦(PC,Personal Computer))之普及率亦提高,處於液晶顯示器之市場日益擴大之狀況。又,近來,如藉由自發光而視認性較高之有機電致發光(EL,Electroluminescence)顯示器之有機發光顯示裝置亦作為下一代圖像顯示裝置而受到關注。於該等圖像顯示裝置之性能中,強烈期望對比度或色再現性之提高等進一步之高畫質化或消耗電力之降低。 In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smart phones, and tablet personal computers (PC, Personal Computer)) is also increasing, and the market for liquid crystal displays is expanding. In addition, recently, organic light-emitting display devices such as organic electroluminescence (EL, Electroluminescence) displays, which are highly visible by self-luminescence, are also attracting attention as next-generation image display devices. In the performance of these image display devices, there is a strong desire for further enhancement of image quality, such as improvement of contrast and color reproducibility, or reduction of power consumption.

於該等液晶顯示裝置或有機發光顯示裝置中使用彩色濾光片。例如液晶顯示裝置之彩色圖像之形成係將通過彩色濾光片之光直接著色為構成彩色濾光片之各像素之顏色,並將該等顏色之光進行合成而形成彩色圖像。作為此時之光源,除了習知之冷陰極管以外,有利用白色發光之有機發光元件或白色發光之無機發光 元件之情況。又,於有機發光顯示裝置中,為了進行顏色調整等而使用彩色濾光片。於此種狀況下,對於彩色濾光片而言,高亮度化或高對比度化、色再現性之提高等期望亦提昇。 Color filters are used in these liquid crystal display devices or organic light emitting display devices. For example, the formation of a color image in a liquid crystal display device directly colors the light passing through the color filter into the color of each pixel constituting the color filter, and synthesizes the light of these colors to form a color image. As the light source at this time, in addition to the conventional cold-cathode tube, there are cases of using white-emitting organic light-emitting elements or white-emitting inorganic light-emitting elements. In addition, in organic light-emitting display devices, color filters are used for color adjustment and the like. Under such circumstances, expectations for color filters, such as higher brightness or higher contrast, and improved color reproducibility, have also increased.

此處,一般而言,彩色濾光片具有:透明基板;著色層,其形成於透明基板上,且包含紅、綠、藍之三原色之著色圖案;及遮光部,其以劃分各著色圖案之方式形成於透明基板上。 Here, in general, the color filter has: a transparent substrate; a coloring layer formed on the transparent substrate and including coloring patterns of the three primary colors of red, green, and blue; and a light-shielding portion that divides the coloring patterns The method is formed on a transparent substrate.

作為彩色濾光片中之像素之形成方法,其中就分光特性、耐久性、圖案形狀及精度等觀點而言,最廣泛地採用平均具有優異特性之顏料分散法。於具有使用顏料分散法形成之像素之彩色濾光片中,為了實現高亮度化或高對比度化,對顏料之微細化進行研究。認為藉由將顏料微細化,可降低由顏料粒子所引起之透過彩色濾光片之光之散射,而達成高亮度化或高對比度化。然而,由於經微細化之顏料粒子容易凝聚,故而有分散性或分散穩定性降低之問題。 As a method of forming pixels in a color filter, among the viewpoints of spectral characteristics, durability, pattern shape and accuracy, the most widely used pigment dispersion method with excellent characteristics on average is used. In a color filter with pixels formed using a pigment dispersion method, in order to achieve high brightness or high contrast, the miniaturization of pigments is studied. It is believed that by miniaturizing the pigment, the scattering of light that passes through the color filter caused by the pigment particles can be reduced, thereby achieving high brightness or high contrast. However, since the micronized pigment particles tend to agglomerate, there is a problem of reduced dispersibility or dispersion stability.

作為提高經微細化之顏料之分散性的方法,已知使用分散劑有效。例如於專利文獻1中,為了滿足經微粒子化之顏料之分散劑的初期分散性及經時分散穩定性,進而亦滿足液晶顯示元件之高對比度化、高亮度性、高顯影性等要求,揭示有一種彩色濾光片用著色組成物,其使用具有A嵌段與B嵌段之嵌段共聚合體作為顏料分散劑,該A嵌段包含具有胺基或銨鹽基之特定之重複單元,該B嵌段包含在羧酸酯之源自醇之部分含有含氧飽和雜環基或烯基之特定之重複單元。又,於專利文獻2中,為了提供可形成色度特性及耐熱性優異之著色層且分散性及保存穩定性良好之彩色濾光片用著色組成物,揭示有一種彩色濾光片用著色組成物,其使 用如下共聚合體作為顏料分散劑,該共聚合體包含具有胺基之特定之重複單元及具有交聯性官能基之重複單元,且胺值為80~250mgKOH/g。 As a method for improving the dispersibility of a finely divided pigment, it is known that the use of a dispersant is effective. For example, in Patent Document 1, in order to satisfy the initial dispersibility and time-dependent dispersion stability of the dispersant of the finely divided pigment, and to meet the requirements of high contrast, high brightness, and high developability of liquid crystal display elements, it is disclosed There is a coloring composition for color filters, which uses a block copolymer having an A block and a B block as a pigment dispersant. The A block contains a specific repeating unit having an amine group or an ammonium salt group. The B block contains specific repeating units containing oxygen-containing saturated heterocyclic groups or alkenyl groups in the alcohol-derived portion of the carboxylic acid ester. In addition, in Patent Document 2, in order to provide a coloring composition for a color filter that can form a colored layer with excellent chromaticity characteristics and heat resistance and has good dispersibility and storage stability, a coloring composition for a color filter is disclosed It uses the following copolymer as a pigment dispersant. The copolymer contains a specific repeating unit with an amine group and a repeating unit with a crosslinkable functional group, and the amine value is 80~250mgKOH/g.

又,於專利文獻3及專利文獻4中,記載有為了獲得色材分散穩定性優異,抑制顯影殘渣產生,並且顯影密接性及溶劑再溶解性優異之感光性著色樹脂組成物,而使用特定之分散劑。作為特定之分散劑,於專利文獻3中記載有一種嵌段共聚合體,其包含具有醯胺基、且具有相當於胺基之末端之氮部位或該氮部位與特定之化合物形成鹽之構造的特定之構成單元,進而具有特定之胺值與特定之玻璃轉移溫度;於專利文獻4中記載有一種嵌段共聚合體,其含有:A嵌段,其包含具有相當於胺基之末端之氮部位或該氮部位與特定之化合物形成鹽之構造的特定之構成單元;及B嵌段,其包含源自含羧基單體之構成單元;該嵌段共聚合體進而具有特定之酸值與特定之玻璃轉移溫度。 In addition, Patent Document 3 and Patent Document 4 describe the use of a specific photosensitive color resin composition in order to obtain a photosensitive colored resin composition that is excellent in color material dispersion stability, suppresses the generation of development residues, and is excellent in development adhesion and solvent resolubility Dispersant. As a specific dispersant, a block copolymer is described in Patent Document 3, which includes a structure having an amide group and a nitrogen site corresponding to the end of the amine group or a structure in which the nitrogen site forms a salt with a specific compound A specific structural unit has a specific amine value and a specific glass transition temperature; Patent Document 4 describes a block copolymer containing: A block, which contains a nitrogen site corresponding to the end of the amine group Or the nitrogen site and the specific compound form a specific structural unit of the structure of the salt; and the B block, which contains the structural unit derived from the carboxyl group-containing monomer; the block copolymer further has a specific acid value and a specific glass Transfer temperature.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

專利文獻1:國際公開第2012/063435號 Patent Document 1: International Publication No. 2012/063435

專利文獻2:日本專利特開2013-88695號公報 Patent Document 2: Japanese Patent Laid-Open No. 2013-88695

專利文獻3:日本專利特開2016-122073號公報 Patent Document 3: Japanese Patent Laid-Open No. 2016-122073

專利文獻4:日本專利特開2016-122169號公報 Patent Document 4: Japanese Patent Laid-Open No. 2016-122169

然而,於近年來之彩色濾光片中,謀求進一步之高亮 度化及各種耐受性之提高。又,一般而言,彩色濾光片係於著色層上形成成為透明電極之氧化銦錫(ITO,Indium Tin Oxide)膜。但是,於習知之彩色濾光片中,亦存在如下問題:於鄰接於著色層上而形成之ITO膜容易產生龜裂,因ITO膜上產生之龜裂而導致電流不流通而產生顯示不良。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能夠形成高亮度之著色層,且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的色材分散液。又,本發明之目的在於提供一種能夠形成高亮度之著色層,且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的該色材分散液所使用之分散劑。又,本發明之目的在於提供一種能夠形成高亮度之著色層,且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的彩色濾光片用感光性著色樹脂組成物。又,本發明之目的在於提供一種使用該彩色濾光片用感光性著色樹脂組成物而形成之彩色濾光片。又,本發明之目的在於提供一種藉由使用該彩色濾光片而顯示特性優異之顯示裝置。 However, in recent color filters, further enhancement of brightness and improvement of various tolerances have been sought. In addition, in general, a color filter is formed on a colored layer to form an indium tin oxide (ITO) (Indium Tin Oxide) film as a transparent electrode. However, in the conventional color filter, there is also the following problem: the ITO film formed adjacent to the colored layer is prone to cracks, and the cracks generated on the ITO film cause current not to flow and display poor display. The present invention was completed in view of the above-mentioned actual situation, and its object is to provide a color material dispersion that can form a high-brightness coloring layer and can suppress cracks in an ITO film formed adjacent to the coloring layer. In addition, an object of the present invention is to provide a dispersant for the color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in the ITO film formed adjacent to the coloring layer. In addition, an object of the present invention is to provide a photosensitive colored resin composition for a color filter that can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. In addition, an object of the present invention is to provide a color filter formed using the photosensitive colored resin composition for a color filter. In addition, an object of the present invention is to provide a display device with excellent display characteristics by using the color filter.

本發明之彩色濾光片用色材分散液係含有色材、分散劑及溶劑者,且上述分散劑係含有A嵌段與B嵌段之嵌段共聚合體,該A嵌段包含下述通式(I)所表示之構成單元,該B嵌段包含選自下述通式(B1)所表示之構成單元及下述通式(B2)所表示之構成單元中之至少一種。 The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of the A block and the B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2).

[化1]

Figure 107106607-A0101-12-0005-5
[化1]
Figure 107106607-A0101-12-0005-5

(通式(I)中,R1表示氫原子或甲基,A表示二價連結基,R2及R3分別獨立地表示氫原子、或可含有雜原子之烴基,R2及R3可相互鍵結而形成環構造。) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R 2 and R 3 can be They are bonded to each other to form a ring structure.)

Figure 107106607-A0101-12-0005-6
Figure 107106607-A0101-12-0005-6

(通式(B1)中,A1表示二價連結基,R11表示可含有氧原子之二、三或四價之脂肪族烴基或碳原子,R10及R12分別獨立地表示氫原子或甲基;n為1、2或3。) (In the general formula (B1), A 1 represents a divalent linking group, R 11 represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R 10 and R 12 each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3.)

[化3]

Figure 107106607-A0101-12-0006-7
[化3]
Figure 107106607-A0101-12-0006-7

(通式(B2)中,A2表示二價連結基,A3及A4分別獨立地表示二、三或四價之連結基,R13表示可含有選自氧原子及氮原子中之至少一種之二價烴基,R14、R16、R18及R19分別獨立地表示可含有氧原子之二價脂肪族烴基,R10、R15及R17分別獨立地表示氫原子或甲基;n1表示0、1、2或3,n2表示0或1,n3表示0、1或2,n1+n2為1、2或3,n1+n2+n3為1、2或3;m1表示1、2或3,m2表示0、1或2,m1+m2為1、2或3。) (In the general formula (B2), A 2 represents a divalent linking group, A 3 and A 4 each independently represent a divalent, trivalent or tetravalent linking group, and R 13 represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R 14 , R 16 , R 18 and R 19 each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R 10 , R 15 and R 17 each independently represent a hydrogen atom or a methyl group; n 1 represents 0, 1, 2 or 3, n 2 represents 0 or 1, n 3 represents 0, 1 or 2, n 1 + n 2 is 1, 2 or 3, n 1 + n 2 + n 3 is 1, 2 or 3; m 1 represents 1, 2 or 3, m 2 represents 0, 1 or 2, and m 1 + m 2 is 1, 2 or 3.)

本發明之分散劑係含有A嵌段與B嵌段之嵌段共聚合體,該A嵌段包含上述通式(I)所表示之構成單元,該B嵌段包含選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種。 The dispersant of the present invention contains a block copolymer of A block and B block, the A block contains the structural unit represented by the above general formula (I), and the B block contains selected from the above general formula (B1) At least one of the structural unit represented and the structural unit represented by the general formula (B2).

本發明之彩色濾光片用感光性著色樹脂組成物含有上述本發明之色材分散液、鹼可溶性樹脂、多官能單體及光起始劑。 The photosensitive colored resin composition for a color filter of the present invention contains the color material dispersion of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator.

本發明之彩色濾光片係至少具備基板及設置於該基板上之著色層者,且該著色層之至少一者為上述本發明之彩色濾光片用感光性著色樹脂組成物之硬化物。 The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition for a color filter of the present invention.

本發明之顯示裝置具有上述本發明之彩色濾光片。 The display device of the present invention has the above-mentioned color filter of the present invention.

根據本發明,可提供一種能夠形成高亮度之著色層且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的色材分散液。又,根據本發明,可提供一種能夠形成高亮度之著色層且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的該色材分散液所使用之分散劑。又,根據本發明,可提供一種能夠形成高亮度之著色層且能夠抑制鄰接於著色層上而形成之ITO膜之龜裂的彩色濾光片用感光性著色樹脂組成物。又,根據本發明,可提供一種使用該彩色濾光片用感光性著色樹脂組成物而形成之彩色濾光片。又,根據本發明,可提供一種藉由使用該彩色濾光片而顯示特性優異之顯示裝置。 According to the present invention, it is possible to provide a color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in an ITO film formed adjacent to the coloring layer. Furthermore, according to the present invention, it is possible to provide a dispersant for the color material dispersion liquid that can form a high-brightness coloring layer and can suppress cracks in the ITO film formed adjacent to the coloring layer. Furthermore, according to the present invention, it is possible to provide a photosensitive colored resin composition for a color filter that can form a high-brightness colored layer and can suppress cracks in an ITO film formed adjacent to the colored layer. Furthermore, according to the present invention, it is possible to provide a color filter formed using the photosensitive colored resin composition for a color filter. Furthermore, according to the present invention, it is possible to provide a display device having excellent display characteristics by using the color filter.

1‧‧‧基板 1‧‧‧Substrate

2‧‧‧遮光部 2‧‧‧Shading part

3‧‧‧著色層 3‧‧‧Coloring layer

10‧‧‧彩色濾光片 10‧‧‧Color filter

20‧‧‧對向基板 20‧‧‧Opposite substrate

30‧‧‧液晶層 30‧‧‧Liquid crystal layer

40‧‧‧液晶顯示裝置 40‧‧‧LCD device

50‧‧‧有機保護層 50‧‧‧Organic protective layer

60‧‧‧無機氧化膜 60‧‧‧Inorganic oxide film

71‧‧‧透明陽極 71‧‧‧Transparent anode

72‧‧‧電洞注入層 72‧‧‧hole injection layer

73‧‧‧電洞傳輸層 73‧‧‧Hole Transmission Layer

74‧‧‧發光層 74‧‧‧Light-emitting layer

75‧‧‧電子注入層 75‧‧‧Electron injection layer

76‧‧‧陰極 76‧‧‧Cathode

80‧‧‧有機發光體 80‧‧‧Organic luminous body

100‧‧‧有機發光顯示裝置 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。 Fig. 1 is a schematic diagram showing an example of the color filter of the present invention.

圖2係表示本發明之液晶顯示裝置之一例之概略圖。 Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.

圖3係表示本發明之有機發光顯示裝置之一例之概略圖。 FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention.

以下,依序對本發明之彩色濾光片用色材分散液、分散劑、彩色濾光片用感光性著色樹脂組成物、彩色濾光片及顯示裝置進行詳細說明。再者,本發明中,光包含可見及非可見區域之波長之電磁波,進而包含放射線,放射線包含例如微波、電子束。具體而言,係指波長5μm以下之電磁波及電子束。本發明中,所謂(甲基)丙烯醯基表示丙烯醯基及甲基丙烯醯基之各者,所謂(甲基)丙烯 酸基表示丙烯酸基及甲基丙烯酸基之各者,所謂(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯之各者。本說明書中,若無特別說明,則色度座標x、y係使用C光源測色之JIS Z8701:1999之XYZ表色系中者。 Hereinafter, the color material dispersion liquid for color filters, the dispersant, the photosensitive colored resin composition for color filters, the color filter, and the display device of the present invention will be described in detail in order. Furthermore, in the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and further includes radiation, which includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves and electron beams with a wavelength of 5 μm or less. In the present invention, the so-called (meth)acryloyl group means each of an acrylic acid group and a methacryloyl group, and the so-called (meth)acrylic group means each of an acrylic group and a methacrylic group, and the so-called (meth)acryloyl group means each of an acrylic acid group and a methacrylic acid group. Acrylate means each of acrylate and methacrylate. In this manual, unless otherwise specified, the chromaticity coordinates x and y are those of the XYZ color system of JIS Z8701: 1999 for color measurement using C light source.

1.彩色濾光片用色材分散液 1. Color material dispersion liquid for color filter

本發明之彩色濾光片用色材分散液係含有色材、分散劑及溶劑者,且上述分散劑係含有A嵌段與B嵌段之嵌段共聚合體,該A嵌段包含下述通式(I)所表示之構成單元,該B嵌段包含選自下述通式(B1)所表示之構成單元及下述通式(B2)所表示之構成單元中之至少一種。 The color material dispersion liquid for color filters of the present invention contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of the A block and the B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2).

Figure 107106607-A0101-12-0008-8
Figure 107106607-A0101-12-0008-8

(通式(I)中,R1表示氫原子或甲基,A表示二價連結基,R2及R3分別獨立地表示氫原子、或可含有雜原子之烴基,R2及R3可相互鍵結而形成環構造。) (In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R 2 and R 3 can be They are bonded to each other to form a ring structure.)

[化5]

Figure 107106607-A0101-12-0009-9
[化5]
Figure 107106607-A0101-12-0009-9

(通式(B1)中,A1表示二價連結基,R11表示可含有氧原子之二、三或四價之脂肪族烴基或碳原子,R10及R12分別獨立地表示氫原子或甲基;n為1、2或3。) (In the general formula (B1), A 1 represents a divalent linking group, R 11 represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R 10 and R 12 each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3.)

Figure 107106607-A0101-12-0009-10
Figure 107106607-A0101-12-0009-10

(通式(B2)中,A2表示二價連結基,A3及A4分別獨立地表示二、三或四價之連結基,R13表示可含有選自氧原子及氮原子中之至少一種之二價烴基,R14、R16、R18及R19分別獨立地表示可含有氧原子之二價脂肪族烴基,R10、R15及R17分別獨立地表示氫原子或甲基;n1表示0、1、2或3,n2表示0或1,n3表示0、1或2,n1+n2為1、2或3,n1+n2+n3為1、2或3;m1表示1、2或3,m2表示0、1或2,m1+m2為1、2或3。) (In the general formula (B2), A 2 represents a divalent linking group, A 3 and A 4 each independently represent a divalent, trivalent or tetravalent linking group, and R 13 represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R 14 , R 16 , R 18 and R 19 each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R 10 , R 15 and R 17 each independently represent a hydrogen atom or a methyl group; n 1 represents 0, 1, 2 or 3, n 2 represents 0 or 1, n 3 represents 0, 1 or 2, n 1 + n 2 is 1, 2 or 3, n 1 + n 2 + n 3 is 1, 2 or 3; m 1 represents 1, 2 or 3, m 2 represents 0, 1 or 2, and m 1 + m 2 is 1, 2 or 3.)

本發明之色材分散液由於使用含有上述特定之A嵌段與上述特定之B嵌段之嵌段共聚合體作為分散劑,因此使用該色材分散液製備之彩色濾光片用感光性著色樹脂組成物可形成高亮度之著色層,可抑制鄰接於著色層上而形成之ITO膜之龜裂。作為發揮此種效果之作用雖不明確,但推斷如下。認為上述特定之嵌段共聚合體藉由A嵌段容易吸附至色材,而提高色材之分散性及分散穩定性,於B嵌段所具有之選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種中,(甲基)丙烯醯基於形成著色層時容易與其他交聯性基交聯。當為習知之分散劑時,色材附近之交聯密度不足,容易因溶劑而產生膨潤。因此,認為於鄰接於著色層上而成膜ITO膜後,因下一步驟中塗佈於ITO膜上之塗佈液中所含之NMP(N-甲基-2-吡咯啶酮)等溶劑,而導致位於ITO膜之下之著色層膨脹,因此容易於作為無機物之ITO膜產生龜裂。與此相對,認為本發明所使用之分散劑藉由B嵌段所具有之選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種所具有之(甲基)丙烯醯基與其他交聯性基進行交聯,尤其於吸附至色材之分散劑之分子間容易進行交聯,而可提高著色層中之色材附近之交聯密度,減少交聯密度變疏之部分,藉此提高膜強度。因此,於本發明中,著色層於色材附近亦可確保交聯密度,可減少交聯密度變疏之部分,藉此抑制由溶劑所引起之膨潤,因此推斷著色層之耐溶劑性優異,不會於鄰接於著色層上而形成之ITO膜產生破裂(龜裂),從而容易形成彩色濾光片。又,著色層中之色材由於成為經交聯密度較高之硬化膜被覆之狀態,故而色材分子之烘烤中之熱運動降低,抑制色材之劣化,因此抑制著色層之亮度之 降低,因此推斷可形成高亮度之著色層。又,認為於側鏈具有選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種的(甲基)丙烯醯基,比起氧雜環丁基等其他交聯性基,與自由基聚合起始劑組合之情況下之光聚合性優異,因此於形成著色層時,藉由曝光可充分地反應而提高交聯密度,於後烘烤時交聯密度較高,藉此可獲得抑制亮度降低之效果,所形成之著色層之亮度進一步提高。又,認為與氧雜環丁基等其他交聯性基相比,(甲基)丙烯醯基於酸或鹼性下之保存穩定性優異,因此與樹脂之酸性基或分散劑之鹼性基共存下之穩定性優異,因此黏度穩定性亦進一步提高。又,於彩色濾光片之製造步驟中,有色材昇華或析出而附著於著色層,成為異物缺陷之原因之情況。若色材自彩色濾光片之著色層昇華,則有如下問題:不僅該著色層之色調發生變化,而且附著於其他著色層等而使其他著色層之色調亦發生變化,導致亮度降低,或產生加熱裝置內之污染。與此相對,本發明藉由使用上述特定之嵌段共聚合體作為分散劑,著色中之色材成為經交聯密度較高之硬化膜被覆之狀態,藉此可抑制色材之昇華及析出。 Since the color material dispersion of the present invention uses a block copolymer containing the above-mentioned specific A block and the above-mentioned specific B block as a dispersant, a photosensitive colored resin for color filters prepared by using the color material dispersion The composition can form a high-brightness coloring layer, and can suppress the cracking of the ITO film formed adjacent to the coloring layer. Although it is unclear as to the effect of exerting this effect, it is estimated as follows. It is believed that the above-mentioned specific block copolymer is easily adsorbed to the color material by the A block, thereby improving the dispersibility and dispersion stability of the color material. The B block has a composition selected from the above-mentioned general formula (B1). Among the units and at least one of the structural units represented by the general formula (B2), the (meth)acrylic acid is easily crosslinked with other crosslinkable groups when forming the colored layer. When it is a conventional dispersant, the crosslinking density near the color material is insufficient, and it is easy to swell due to the solvent. Therefore, it is considered that after the ITO film is formed adjacent to the colored layer, the solvent such as NMP (N-methyl-2-pyrrolidone) contained in the coating solution applied on the ITO film in the next step , Causing the coloring layer under the ITO film to swell, so it is easy to crack in the ITO film, which is an inorganic substance. On the contrary, it is considered that the dispersant used in the present invention is composed of at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) possessed by the B block. The (meth)acrylic acid group is cross-linked with other cross-linkable groups, especially the intermolecular of the dispersant adsorbed to the color material is easily cross-linked, which can increase the cross-linking density near the color material in the color layer , Reduce the part where the cross-linking density becomes thinner, thereby increasing the strength of the film. Therefore, in the present invention, the colored layer in the vicinity of the color material can also ensure the cross-linking density, reducing the part where the cross-linking density becomes sparse, and thereby suppressing the swelling caused by the solvent. Therefore, it is inferred that the colored layer has excellent solvent resistance. The ITO film formed adjacent to the colored layer will not be cracked (crack), so that the color filter can be easily formed. In addition, since the color material in the color layer is covered by a cured film with a higher crosslinking density, the thermal movement of the color material molecules during baking is reduced, and the deterioration of the color material is suppressed, thereby suppressing the decrease in the brightness of the color layer. , So it is inferred that a high-brightness colored layer can be formed. In addition, it is considered that a (meth)acryloyl group having at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) in the side chain is more than an oxygen heterocyclic ring Other cross-linking groups such as butyl have excellent photopolymerization when combined with a radical polymerization initiator. Therefore, when the colored layer is formed, it can react sufficiently by exposure to increase the cross-linking density and post-baking When the crosslinking density is higher, the effect of suppressing the decrease in brightness can be obtained, and the brightness of the formed coloring layer is further improved. In addition, it is believed that compared with other crosslinkable groups such as oxetanyl group, (meth)acrylic acid has excellent storage stability under acid or alkalinity, so it coexists with the acidic group of the resin or the basic group of the dispersant. The stability below is excellent, so the viscosity stability is further improved. In addition, in the manufacturing process of the color filter, the colored material sublimates or precipitates and adheres to the colored layer, which may cause foreign matter defects. If the color material is sublimated from the coloring layer of the color filter, there will be the following problems: not only the hue of the colored layer changes, but the hue of other colored layers is also changed due to adhesion to other colored layers, resulting in a decrease in brightness, or Produce pollution in the heating device. In contrast, in the present invention, by using the above-mentioned specific block copolymer as a dispersant, the color material in coloring becomes a state covered by a cured film with a higher crosslinking density, thereby suppressing the sublimation and precipitation of the color material.

本發明之色材分散液係至少含有色材、分散劑及溶劑者,亦可於無損本發明之效果之範圍內進而含有其他成分。以下,對此種本發明之色材分散液之各成分,自本發明之分散劑起依序進行詳細說明。 The color material dispersion liquid of the present invention contains at least a color material, a dispersant, and a solvent, and may further contain other components within a range that does not impair the effects of the present invention. Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail sequentially starting from the dispersant of the present invention.

<分散劑> <Dispersant>

於本發明中,使用含有A嵌段與B嵌段之嵌段共聚合體作為分散劑,該A嵌段包含上述通式(I)所表示之構成單元,該B嵌段 包含選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種。該嵌段共聚合體亦可由上述通式(I)所表示之構成單元所具有之末端之氮部位之至少一部分與選自由有機酸化合物及鹵代烴所構成之群中之至少一種形成鹽(以下有時稱為鹽型嵌段共聚合體)。首先,自嵌段共聚合體進行說明。 In the present invention, a block copolymer containing an A block and a B block is used as a dispersant. The A block contains the structural unit represented by the above general formula (I), and the B block contains selected from the above general formula. At least one of the structural unit represented by (B1) and the structural unit represented by the above general formula (B2). The block copolymer may also be formed from at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons (hereinafter Sometimes called salt block copolymer). First, the self-block copolymer will be described.

{A嵌段} {A block}

(通式(I)所表示之構成單元) (Constituted unit represented by general formula (I))

A嵌段中所包含之上述通式(I)所表示之構成單元具有鹼性,作為對色材之吸附部位發揮功能。於通式(I)中,A為二價連結基。作為二價連結基,例如可列舉:碳原子數1~10之伸烷基、伸芳基、-CONH-基、-COO-基、碳原子數1~10之醚基(-R'-OR"-:R'及R"分別獨立為伸烷基)及該等之組合等。其中,就分散性之方面而言,通式(I)中之A較佳為包含-CONH-基或-COO-基之二價連結基。 The structural unit represented by the above general formula (I) contained in the A block has basicity and functions as an adsorption site for the color material. In the general formula (I), A is a divalent linking group. As the divalent linking group, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms (-R'-OR "-: R'and R" are each independently an alkylene group) and combinations thereof. Among them, in terms of dispersibility, A in the general formula (I) is preferably a divalent linking group including a -CONH- group or a -COO- group.

R2及R3中之可含有雜原子之烴基中之烴基例如可列舉烷基、芳烷基、芳基等。作為烷基,例如可列舉:甲基、乙基、丙基、丁基、異丙基、第三丁基、2-乙基己基、環戊基、環己基等,烷基之碳原子數較佳為1~18,其中更佳為甲基或乙基。作為芳烷基,例如可列舉:苄基、苯乙基、萘基甲基、聯苯基甲基等。芳烷基之碳原子數較佳為7~20,進而較佳為7~14。又,作為芳基,可列舉苯基、聯苯基、萘基、甲苯基、二甲苯基等。芳基之碳原子數較佳為6~24,進而較佳為6~12。再者,上述較佳之碳原子數不包含取代基之碳原子數。含有雜原子之烴基具有上述烴基中之碳原子經雜原子取代之構造。作為烴基可含有之雜原子,例如可列舉 氧原子、氮原子、硫原子、矽原子等。又,烴基中之氫原子可經碳原子數1~5之烷基、氟原子、氯原子、溴原子等鹵素原子取代。 Examples of the hydrocarbon group in the hydrocarbon group that may contain a hetero atom in R 2 and R 3 include an alkyl group, an aralkyl group, and an aryl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, isopropyl, tertiary butyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, etc. The number of carbon atoms in the alkyl group is relatively high. Preferably it is 1-18, and more preferably is methyl or ethyl. As an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, for example. The number of carbon atoms of the aralkyl group is preferably 7-20, and more preferably 7-14. Moreover, as an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. The number of carbon atoms of the aryl group is preferably 6-24, and more preferably 6-12. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent. The heteroatom-containing hydrocarbon group has a structure in which the carbon atoms in the above-mentioned hydrocarbon group are substituted by heteroatoms. Examples of the hetero atom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In addition, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom.

所謂R2與R3可相互鍵結而形成環構造係指R2與R3經由氮原子而形成環構造。R2及R3所形成之環構造中可含有雜原子。環構造並無特別限定,例如可列舉吡咯啶環、哌啶環、

Figure 107106607-A0101-12-0013-29
啉環等。 The phrase that R 2 and R 3 may be bonded to each other to form a ring structure means that R 2 and R 3 form a ring structure via a nitrogen atom. The ring structure formed by R 2 and R 3 may contain heteroatoms. The ring structure is not particularly limited, and examples include pyrrolidine ring, piperidine ring,
Figure 107106607-A0101-12-0013-29
Morpholino ring etc.

於本發明中,其中較佳為R2與R3分別獨立為氫原子、碳原子數1~5之烷基、苯基,或R2與R3鍵結而形成吡咯啶環、哌啶環、

Figure 107106607-A0101-12-0013-30
啉環。 In the present invention, it is preferred that R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 2 and R 3 are bonded to form a pyrrolidine ring or a piperidine ring ,
Figure 107106607-A0101-12-0013-30
Morpholino ring.

作為衍生上述通式(I)所表示之構成單元之單體,可列舉:(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二甲胺基丙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二乙胺基丙酯等含有烷基取代胺基之(甲基)丙烯酸酯等、二甲胺基乙基(甲基)丙烯醯胺、二甲胺基丙基(甲基)丙烯醯胺等含有烷基取代胺基之(甲基)丙烯醯胺等。其中,就提高分散性及分散穩定性之方面而言,較佳可使用(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、二甲胺基丙基(甲基)丙烯醯胺。通式(I)所表示之構成單元可為由1種構成者,亦可為包含2種以上之構成單元者。 Examples of monomers that derive the constituent units represented by the above general formula (I) include: dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethyamine (meth)acrylate. Ethylaminoethyl, diethylaminopropyl (meth)acrylate, etc. (meth)acrylates containing alkyl substituted amino groups, etc., dimethylaminoethyl (meth)acrylamide, dimethylamine Alkylpropyl (meth)acrylamide, etc., containing alkyl-substituted amino group (meth)acrylamide, etc. Among them, in terms of improving dispersibility and dispersion stability, it is preferable to use dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate ( (Meth)acrylamide. The structural unit represented by the general formula (I) may be composed of one type, or may be composed of two or more types of structural units.

於包含通式(I)所表示之構成單元之A嵌段中,通式(I)所表示之構成單元較佳為包含3個以上。其中,就提高分散性及分散穩定性之方面而言,較佳為包含3~100個,更佳為包含3~50個,進而更佳為包含3~30個。 In the A block containing the structural unit represented by the general formula (I), the structural unit represented by the general formula (I) preferably contains 3 or more. Among them, in terms of improving dispersibility and dispersion stability, it is preferable to include 3 to 100, more preferably 3 to 50, and even more preferably 3 to 30.

A嵌段亦可於達成本發明之目的之範圍內具有通式(I)所表示之構成單元以外之構成單元,只要為能夠與通式(I)所表示之 構成單元共聚合之構成單元便可含有。例如作為A嵌段亦可含有之除通式(I)所表示之構成單元以外之構成單元,可使用下述B嵌段中所列舉之「其他構成單元」,具體而言,例如可列舉下述通式(II)所表示之構成單元等。於鹽形成前之嵌段共聚合體中之A嵌段中,通式(I)所表示之構成單元之含有比率較佳為相對於A嵌段之總構成單元之合計質量為50~100質量%,更佳為80~100質量%,最佳為100質量%。其原因在於,通式(I)所表示之構成單元之比率越高,對色材之吸附力越提高,嵌段共聚合體之分散性、及分散穩定性越良好。再者,上述構成單元之含有比率係由合成具有通式(I)所表示之構成單元之A嵌段時之饋入質量算出。 The A block may have a structural unit other than the structural unit represented by the general formula (I) within the scope of achieving the purpose of the invention, as long as it is a structural unit that can be copolymerized with the structural unit represented by the general formula (I) May contain. For example, as a structural unit other than the structural unit represented by the general formula (I) that may be contained in the A block, the "other structural units" listed in the following B block can be used. Specifically, for example, the following The structural units represented by the general formula (II), etc. are described. In the A block in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably 50-100% by mass relative to the total mass of the total structural unit of the A block , More preferably 80-100% by mass, most preferably 100% by mass. The reason is that the higher the ratio of the constituent units represented by the general formula (I), the higher the adsorption force to the color material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when synthesizing the A block having the structural unit represented by the general formula (I).

又,就分散性及分散穩定性變得良好之方面而言,於鹽形成前之嵌段共聚合體中,通式(I)所表示之構成單元之含有比率較佳為相對於嵌段共聚合體之總構成單元之合計質量為5~60質量%,更佳為10~50質量%。再者,上述嵌段共聚合體中之各構成單元之含有比率係由合成鹽形成前之嵌段共聚合體時之饋入質量而算出。再者,通式(I)所表示之構成單元只要具有與色材之親和性即可,可為由1種構成者,亦可包含2種以上之構成單元。 Moreover, in terms of improving dispersibility and dispersion stability, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (I) is preferably relative to the block copolymer The total mass of the total constituent units is 5-60% by mass, more preferably 10-50% by mass. In addition, the content ratio of each constituent unit in the above-mentioned block copolymer is calculated from the feed mass at the time of synthesizing the block copolymer before formation of the salt. Furthermore, the structural unit represented by the general formula (I) only needs to have affinity with the color material, and may be composed of one type, or may include two or more types of structural units.

{B嵌段} {B block}

B嵌段係不含上述通式(I)所表示之構成單元,而含有選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種之嵌段,且亦可於無損本發明之效果之範圍內進而含有其他構成單元之嵌段。作為B嵌段,就分散性及分散穩定性之方面而言,較佳為使用自能夠與衍生通式(I)所表示之構成單元之單體共聚 合之具有不飽和雙鍵之單體中以具有親溶劑性之方式根據溶劑適當選擇而構成之嵌段。作為標準,較佳為相對於組合使用之溶劑,以共聚合體之23℃下之溶解度成為20(g/100g溶劑)以上之方式導入B嵌段。 The B block does not contain the structural unit represented by the general formula (I), but contains at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) Blocks, and may further contain blocks of other constituent units within a range that does not impair the effects of the present invention. As the B block, in terms of dispersibility and dispersion stability, it is preferable to use a monomer having an unsaturated double bond that can be copolymerized with a monomer that derives the constituent unit represented by the general formula (I) The block is appropriately selected according to the solvent so as to have a solvophilic property. As a standard, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. becomes 20 (g/100g solvent) or more with respect to the solvent used in combination.

(選自通式(B1)所表示之構成單元及通式(B2)所表示之構成單元中之至少一種) (At least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2))

B嵌段包含選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種。作為上述通式(B1)之A1以及上述通式(B2)之A2、A3及A4中之二價連結基、A3及A4中之三價或四價之連結基,例如表示脂肪族烴基、芳香族基、-CONH-基、-COO-基、及該等之組合,可於碳鏈中含有O(氧原子)、S(硫原子)、N(氮原子),亦可具有取代基。作為上述四價連結基,亦可為碳原子。A1、A2、A3及A4中之脂肪族烴基可為直鏈、支鏈或環狀之飽和或不飽和之任一者,可具有取代基,亦可於碳鏈中具有O、S、N等雜原子。例如亦可於碳鏈中含有醚基、硫醚基、羰基、氧基羰基、醯胺基等。又,作為上述取代基,可列舉鹵素原子、烷氧基、苯氧基等。A1、A2、A3及A4中之芳香族基可列舉單環或多環芳香族基,可具有取代基,亦可為含有O、S、N之雜環。作為芳香族基,例如可列舉含有苯環、萘環之基,其中較佳為含有苯環之基。作為取代基,可列舉與上述相同者。作為A1、A2、A3及A4中之脂肪族烴基與芳香族基之組合,可列舉上述脂肪族烴基與上述芳香族基直接鍵結之構造、或上述脂肪族烴基與上述芳香族基以上述醚基等含有雜原子之連結基連結之構造。作為上述通式(B1)之A1及上述通式 (B2)之A2中之二價連結基,其中較佳為含有-COO-基與碳原子數1~10之伸烷基之二價連結基,更佳為作為-COO-基與碳原子數1~10之伸烷基之組合之二價連結基。作為上述通式(B2)之A3及A4中之二價連結基,其中較佳為碳原子數1~10之伸烷基。上述通式(B1)之A1、以及上述通式(B2)之A2、A3及A4中之伸烷基可為直鏈狀、支鏈狀、環狀之任一者,較佳為直鏈狀。又,該伸烷基可具有取代基,亦可於碳鏈中含有O、S、N等雜原子。作為上述通式(B2)之A3及A4中之三價連結基,其中較佳為自碳原子數1~10之脂肪族飽和烴去除3個氫原子後之剩餘之原子團,更佳為自碳原子數1~5之脂肪族飽和烴去除3個氫原子後之剩餘之原子團。該等脂肪族飽和烴基可具有取代基,亦可於碳鏈中含有O、S、N等雜原子。作為上述通式(B2)之A3及A4中之四價連結基,其中較佳為自碳原子數1~10之脂肪族飽和烴去除4個氫原子後之剩餘之原子團或碳原子,更佳為自碳原子數1~5之脂肪族飽和烴去除4個氫原子後之剩餘之原子團或碳原子。該等脂肪族飽和烴基可具有取代基,亦可於碳鏈中含有O、S、N等雜原子。 The B block contains at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2). As the bivalent linking group in A 1 of the above general formula (B1) and A 2 , A 3 and A 4 of the above general formula (B2), the trivalent or tetravalent linking group in A 3 and A 4, for example Represents aliphatic hydrocarbon groups, aromatic groups, -CONH- groups, -COO- groups, and combinations of these, and can contain O (oxygen atom), S (sulfur atom), N (nitrogen atom) in the carbon chain, and also May have substituents. As the above-mentioned tetravalent linking group, it may be a carbon atom. The aliphatic hydrocarbon groups in A 1 , A 2 , A 3 and A 4 may be linear, branched, or cyclic, saturated or unsaturated, may have substituents, and may also have O, S, N and other heteroatoms. For example, an ether group, a thioether group, a carbonyl group, an oxycarbonyl group, an amide group, etc. may be contained in the carbon chain. Moreover, as the above-mentioned substituent, a halogen atom, an alkoxy group, a phenoxy group, etc. are mentioned. The aromatic group in A 1 , A 2 , A 3 and A 4 may be a monocyclic or polycyclic aromatic group, which may have a substituent, and may also be a heterocyclic ring containing O, S, and N. The aromatic group includes, for example, a group containing a benzene ring and a naphthalene ring, and among these, a group containing a benzene ring is preferred. As a substituent, the same thing as mentioned above can be mentioned. Examples of the combination of aliphatic hydrocarbon groups and aromatic groups in A 1 , A 2 , A 3 and A 4 include a structure in which the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic group are directly bonded, or the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic group. The structure is connected with a heteroatom-containing linking group such as the above-mentioned ether group. Examples of the formula (B1) of the general formula A 1 and (B2) of A 2 in the divalent linking group, which is preferably a divalent group with the number of carbon atoms -COO- extending alkyl group having 1 to 10 of the The linking group is more preferably a divalent linking group that is a combination of a -COO- group and an alkylene group having 1 to 10 carbon atoms. As the divalent linking group in A 3 and A 4 of the general formula (B2), among them, an alkylene group having 1 to 10 carbon atoms is preferred. The A 1 of the above general formula (B1) and the alkylenes of A 2 , A 3 and A 4 of the above general formula (B2) may be linear, branched, or cyclic, preferably It is linear. In addition, the alkylene group may have a substituent, and may contain heteroatoms such as O, S, and N in the carbon chain. As the trivalent linking group in A 3 and A 4 of the above general formula (B2), the group of atoms remaining after removing 3 hydrogen atoms from a saturated aliphatic hydrocarbon with 1 to 10 carbon atoms is preferred, and more preferred is The group of atoms remaining after removing 3 hydrogen atoms from saturated aliphatic hydrocarbons with 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have substituents, and may contain heteroatoms such as O, S, and N in the carbon chain. As the tetravalent linking group in A 3 and A 4 of the above general formula (B2), the atom group or carbon atom remaining after removing 4 hydrogen atoms from the aliphatic saturated hydrocarbon with 1 to 10 carbon atoms is preferred, More preferably, it is the atom group or carbon atom remaining after 4 hydrogen atoms are removed from the aliphatic saturated hydrocarbon with 1 to 5 carbon atoms. These aliphatic saturated hydrocarbon groups may have substituents, and may contain heteroatoms such as O, S, and N in the carbon chain.

作為上述通式(B2)之R13中之可含有選自氧原子及氮原子中之至少一種之二價烴基,可為脂肪族烴基或芳香族烴基之任一者,例如可列舉可含有選自氧原子及氮原子中之至少一種之直鏈、支鏈或環狀之伸烷基及伸烯基、伸芳基、以及該等之組合,亦可於碳鏈中含有-CONH-基、-COO-基、醚基等。 As the divalent hydrocarbon group in R 13 of the above general formula (B2), which may contain at least one selected from an oxygen atom and a nitrogen atom, it may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. For example, it may contain Linear, branched or cyclic alkylene, alkenylene, arylene, and combinations of at least one of oxygen atom and nitrogen atom may also contain -CONH- group in the carbon chain, -COO- group, ether group, etc.

作為上述通式(B1)之R11以及上述通式(B2)之R14、R16、R18及R19中之可含有氧原子之二價脂肪族烴基,例如可列舉直鏈、支鏈或環狀之伸烷基及伸烯基,亦可於碳鏈中含有醚基等。 其中,較佳為可含有氧原子之碳原子數1~10之伸烷基。再者,於上述通式(B2)中具有數個R14、R16、R18或R19之情況下,數個R14、數個R16、數個R18及數個R19可分別相同亦可不同。又,作為上述通式(B1)之R11中之可含有氧原子之三價或四價之脂肪族烴基,例如可列舉自直鏈、支鏈或環狀之脂肪族飽和烴或脂肪族不飽和烴去除3個或4個氫原子後之剩餘之脂肪族烴基或碳原子,亦可於碳鏈中含有醚基等。其中,較佳為自可含有氧原子之碳原子數1~10之直鏈、支鏈或環狀之脂肪族飽和烴去除3個或4個氫原子後之剩餘之脂肪族飽和烴基或碳原子。 Examples of the divalent aliphatic hydrocarbon groups that may contain oxygen atoms in R 11 of the above general formula (B1) and R 14 , R 16 , R 18 and R 19 of the above general formula (B2) include straight chain and branched chain Or cyclic alkylene and alkenylene groups, and may also contain ether groups in the carbon chain. Among them, an alkylene group having 1 to 10 carbon atoms which may contain an oxygen atom is preferred. Furthermore, when there are several R 14 , R 16 , R 18 or R 19 in the above general formula (B2), several R 14 , several R 16 , several R 18 and several R 19 can be respectively The same may be different. In addition, as the trivalent or tetravalent aliphatic hydrocarbon group in R 11 of the above general formula (B1) that may contain an oxygen atom, for example, aliphatic saturated hydrocarbons or aliphatic non-linear, branched, or cyclic aliphatic hydrocarbon groups may be included. The remaining aliphatic hydrocarbon groups or carbon atoms after the removal of 3 or 4 hydrogen atoms in saturated hydrocarbons may also contain ether groups in the carbon chain. Among them, it is preferably the aliphatic saturated hydrocarbon group or carbon atom remaining after removing 3 or 4 hydrogen atoms from linear, branched or cyclic aliphatic saturated hydrocarbons with 1 to 10 carbon atoms that may contain oxygen atoms .

作為上述通式(B1)之R10及R12、以及上述通式(B2)之R10、R15及R17,其中,就反應性較高,提高膜強度,提高著色層之亮度及ITO膜之耐龜裂性之方面而言,較佳為氫原子。再者,於上述通式(B1)中具有數個R12之情況、及於上述通式(B2)中具有數個R15或R17之情況下,數個R12、數個R15及數個R17可分別相同亦可不同。 As R 10 and R 12 of the above general formula (B1) and R 10 , R 15 and R 17 of the above general formula (B2), among them, the reactivity is higher, the film strength is improved, the brightness of the colored layer and the ITO are improved In terms of the crack resistance of the film, a hydrogen atom is preferred. Furthermore, in the case where there are several R 12 in the above general formula (B1) and in the case where there are several R 15 or R 17 in the above general formula (B2), several R 12 , several R 15 and The plurality of R 17 may be the same or different.

於上述通式(B2)中,就分散劑之羥值容易變得適當之方面、溶劑再溶解性及顯影密接性之方面、以及亮度及ITO膜之耐龜裂性之方面而言,較佳為n1+n2>n3,又,較佳為m1>m2In the above general formula (B2), it is preferable in terms of the hydroxy value of the dispersant easily becomes appropriate, in terms of solvent resolubility and development adhesion, and in terms of brightness and crack resistance of the ITO film. It is n 1 +n 2 >n 3 , and preferably m 1 >m 2 .

於側鏈具有選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種的(甲基)丙烯醯基之個數並無特別限定,就提高ITO膜之耐龜裂性之方面而言,較佳為2個以上,另一方面,就分散穩定性之方面而言,較佳為6個以下,更佳為3個以下,亦可為1個或2個。 The number of (meth)acrylic groups having at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) in the side chain is not particularly limited, as long as In terms of improving the crack resistance of the ITO film, two or more are preferred. On the other hand, in terms of dispersion stability, it is preferably 6 or less, more preferably 3 or less, or 1 or 2.

選自上述通式(B1)所表示之構成單元及上述通式(B2) 所表示之構成單元中之至少一種例如可藉由使用具有能夠與衍生通式(I)所表示之構成單元之單體共聚合之不飽和雙鍵與羥基之單體(以下稱為「含羥基之單體」),導入具有羥基之構成單元,使具有異氰酸基與(甲基)丙烯醯基之化合物(以下稱為「含異氰酸基之(甲基)丙烯酸酯」)之異氰酸基與上述構成單元中之羥基進行反應而導入。又,上述通式(B2)所表示之構成單元例如亦可藉由使用含羥基之單體導入具有羥基之構成單元,使二異氰酸酯化合物之一異氰酸基與上述構成單元中之羥基進行反應,使二異氰酸酯化合物之另一異氰酸基與具有羥基及(甲基)丙烯醯基之化合物之羥基進行反應而導入。再者,此處之羥基係指鍵結於脂肪族烴之醇性羥基。羥基與異氰酸基之反應性較高,可將反應溫度降低為70~90℃左右,無需使用胺系觸媒,因此藉由利用上述方法導入選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種,可抑制因反應時之加熱或觸媒所引起之黃變,因此亦可抑制著色層之黃變,可提高著色層之亮度。又,於上述導入方法中,可容易地調整羥值,因此可藉由使羥值成為適當之值而提高溶劑再溶解性等。 At least one selected from the structural unit represented by the above-mentioned general formula (B1) and the structural unit represented by the above-mentioned general formula (B2) can be used, for example, by using a single unit having the structural unit represented by the general formula (I). Monomer copolymerized unsaturated double bonds and hydroxyl monomers (hereinafter referred to as "hydroxyl-containing monomers"), introducing structural units having hydroxyl groups to make compounds having isocyanate groups and (meth)acrylic groups ( Hereinafter, the isocyanate group referred to as "isocyanate group-containing (meth)acrylate") reacts with the hydroxyl group in the above-mentioned structural unit to be introduced. In addition, the structural unit represented by the above-mentioned general formula (B2) may be used, for example, by using a hydroxyl-containing monomer to introduce a structural unit having a hydroxyl group, so that an isocyanate group of the diisocyanate compound can react with the hydroxyl group in the above-mentioned structural unit. , The other isocyanate group of the diisocyanate compound is introduced by reacting with the hydroxyl group of the compound having a hydroxyl group and a (meth)acryloyl group. Furthermore, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon. The reactivity of the hydroxyl group and the isocyanate group is high, and the reaction temperature can be reduced to about 70~90°C without the use of an amine catalyst. Therefore, the composition selected from the general formula (B1) is introduced by the above method At least one of the unit and the structural unit represented by the above general formula (B2) can inhibit yellowing caused by heating or catalyst during the reaction, so it can also inhibit the yellowing of the colored layer and improve the brightness of the colored layer . In addition, in the above-mentioned introduction method, the hydroxyl value can be easily adjusted, so that the solvent resolubility can be improved by making the hydroxyl value an appropriate value.

作為上述含羥基之單體,只要為具有能夠與衍生通式(I)所表示之構成單元之單體共聚合之不飽和雙鍵與至少具一個羥基之單體,則無特別限定,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2(或3)-羥基丙酯、(甲基)丙烯酸2(或3或4)-羥基丁酯、環己烷二甲醇單(甲基)丙烯酸酯等(甲基)丙烯酸羥基烷基酯、丙烯酸乙基-α-羥基甲酯等丙烯酸烷基-α-羥基烷基酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等(甲基)丙烯酸羥基芳氧基烷基酯、(甲基)丙 烯酸羥基烷氧基烷基酯、甘油單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基乙酯之ε-己內酯1莫耳加成物等具有羥基之(甲基)丙烯酸酯系單體;N-(2-羥基乙基)(甲基)丙烯醯胺、N-(2-羥基丙基)(甲基)丙烯醯胺、N-(2-羥基丁基)(甲基)丙烯醯胺等N-(羥基烷基)(甲基)丙烯醯胺等具有羥基之(甲基)丙烯醯胺系單體;2-羥基乙基乙烯醚、2-(或3-)羥基丙基乙烯醚、2-(或3-或4-)羥基丁基乙烯醚等羥基烷基乙烯醚等具有羥基之乙烯醚系單體;2-羥基乙基烯丙醚、2-(或3-)羥基丙基烯丙醚、2-(或3-或4-)羥基丁基烯丙醚等羥基烷基烯丙醚等具有羥基之烯丙醚系單體等,其中較佳為具有羥基之(甲基)丙烯酸酯系單體,就提高顯影性之方面而言,具有一級羥基優於具有二級羥基。再者,所謂一級羥基係指羥基鍵結之碳原子為一級碳原子之羥基,所謂二級羥基係指羥基鍵結之碳原子為二級碳原子之羥基。又,就提高顯影密接性之方面而言,其中較佳為使用各單體之均聚物之玻璃轉移溫度之值(Tgi)成為0℃以上之含羥基之單體,進而較佳為使用成為10℃以上之含羥基之單體。作為具有羥基之(甲基)丙烯酸酯系單體,更佳為選自(甲基)丙烯酸羥基烷基酯、(甲基)丙烯酸羥基芳基烷基酯、(甲基)丙烯酸羥基烷氧基烷基酯及(甲基)丙烯酸羥基芳氧基烷基酯中之至少一種,進而更佳為選自(甲基)丙烯酸羥基烷基酯及(甲基)丙烯酸羥基芳氧基烷基酯中之至少一種,尤佳為選自由(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁酯及(甲基)丙烯酸2-羥基-3-苯氧基丙酯所構成之群中之1種以上。 The hydroxyl-containing monomer is not particularly limited as long as it has an unsaturated double bond that can be copolymerized with the monomer deriving the structural unit represented by the general formula (I) and a monomer having at least one hydroxyl group. For example, Examples: 2-hydroxyethyl (meth)acrylate, 2(or 3)-hydroxypropyl (meth)acrylate, 2(or 3 or 4)-hydroxybutyl (meth)acrylate, cyclohexane dimethanol Hydroxyalkyl (meth)acrylates such as mono(meth)acrylate, alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, 2-hydroxy-3-(meth)acrylate Phenoxypropyl ester and other hydroxyaryloxyalkyl (meth)acrylate, hydroxyalkoxyalkyl (meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth) Acrylate, ε-caprolactone 1 mol adduct of 2-hydroxyethyl (meth)acrylate and other (meth)acrylate monomers with hydroxyl groups; N-(2-hydroxyethyl)(former N-(hydroxyalkyl)(methyl)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, etc. ) (Meth)acrylamide monomers having hydroxyl groups such as acrylamide; 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, 2-(or 3- or 4-) Hydroxyalkyl vinyl ethers and other vinyl ether monomers such as hydroxybutyl vinyl ether; 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, 2-(or 3- Or 4-) Allyl ether monomers having hydroxyl groups such as hydroxyalkyl allyl ethers such as hydroxybutyl allyl ether, etc. Among them, (meth)acrylate monomers having hydroxyl groups are preferred to improve developability In terms of it, having a primary hydroxyl group is better than having a secondary hydroxyl group. Furthermore, the so-called primary hydroxyl group refers to a hydroxyl group whose carbon atom to which the hydroxyl group is bonded is a primary carbon atom, and the so-called secondary hydroxyl group refers to a hydroxyl group whose carbon atom to which the hydroxyl group is bonded is a secondary carbon atom. Moreover, in terms of improving the adhesiveness of development, among them, it is preferable to use the value of the glass transition temperature (Tgi) of the homopolymer of each monomer to be a hydroxyl-containing monomer of 0°C or higher, and it is more preferable to use it as Hydroxyl-containing monomers above 10°C. The (meth)acrylate monomer having a hydroxyl group is more preferably selected from hydroxyalkyl (meth)acrylate, hydroxyarylalkyl (meth)acrylate, and hydroxyalkoxy (meth)acrylate At least one of alkyl ester and hydroxyaryloxyalkyl (meth)acrylate, and more preferably selected from hydroxyalkyl (meth)acrylate and hydroxyaryloxyalkyl (meth)acrylate At least one of them, particularly preferably selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate More than one species in the group.

作為導入上述通式(B1)所表示之構成單元時使用之上述含異氰酸基之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸2- 異氰酸基乙酯、(甲基)丙烯酸3-異氰酸基丙酯、(甲基)丙烯酸2-異氰酸基-1-甲基乙酯、(甲基)丙烯酸2-異氰酸基-1,1-二甲基乙酯、(甲基)丙烯酸4-異氰酸基環己酯、(甲基)丙烯酸2-(2-異氰酸基乙氧基)乙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯及該等之衍生物等。作為上述衍生物,例如可列舉具有經封端劑遮蔽之異氰酸基與至少一個(甲基)丙烯醯基之化合物,例如可列舉甲基丙烯酸2-[(3,5-二甲基吡唑基)羰基胺基]乙酯、甲基丙烯酸2-(0-[1'-甲基亞丙基胺基]羧基胺基)乙酯等。作為該等之市售品,例如可列舉:Karenz AOI(註冊商標)、Karenz MOI(註冊商標)、AOI-VM(註冊商標)、Karenz MOI-EG(註冊商標)、Karenz BEI(註冊商標)、Karenz MOI-BP(註冊商標)、Karenz MOI-BM(註冊商標)(以上為昭和電工股份有限公司製造)等。 Examples of the above-mentioned isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the above-mentioned general formula (B1) include: 2-isocyanatoethyl (meth)acrylate, (former) Base) 3-isocyanatopropyl acrylate, 2-isocyanato-1-methyl ethyl (meth)acrylate, 2-isocyanato-1,1-dimethyl (meth)acrylate Ethyl, 4-isocyanatocyclohexyl (meth)acrylate, 2-(2-isocyanatoethoxy)ethyl (meth)acrylate, 1,1-(bisacrylic acid) isocyanate (Oxymethyl) ethyl ester and their derivatives. Examples of the above-mentioned derivatives include compounds having an isocyanate group and at least one (meth)acryloyl group blocked by a blocking agent, such as 2-[(3,5-dimethylpyridine methacrylate). Azolyl)carbonylamino]ethyl, 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate and the like. Examples of these commercially available products include: Karenz AOI (registered trademark), Karenz MOI (registered trademark), AOI-VM (registered trademark), Karenz MOI-EG (registered trademark), Karenz BEI (registered trademark), Karenz MOI-BP (registered trademark), Karenz MOI-BM (registered trademark) (the above are made by Showa Denko Co., Ltd.), etc.

作為導入上述通式(B2)所表示之構成單元時使用之上述含異氰酸基之(甲基)丙烯酸酯,例如可列舉含羥基之(甲基)丙烯酸酯與二異氰酸酯化合物之莫耳比約1:1之反應產物。作為上述反應產物中之含羥基之(甲基)丙烯酸酯,例如可列舉能夠作為上述含羥基之單體使用之上述具有羥基之(甲基)丙烯酸酯系単體、及含羥基之多官能(甲基)丙烯酸酯。含羥基之多官能(甲基)丙烯酸酯係具有至少一個羥基及2個以上之(甲基)丙烯醯基之化合物,並無特別限定,較佳為具有1~4個羥基且具有2~5個(甲基)丙烯醯基者。作為含羥基之多官能(甲基)丙烯酸酯之具體例,例如可列舉:三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇之二或三(甲基)丙烯酸酯、二季戊四醇之二、三、四或五(甲基)丙烯酸酯等。作為二異氰酸酯化合物,例如可列舉:六亞甲基二異氰酸酯、2,4-或2,6-甲苯 二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、異氰酸3,5,5-三甲基-3-異氰酸基甲基環己酯、間或對苯二甲基二異氰酸酯、1,3-或1,4-雙(異氰酸基甲基)環己烷、離胺酸二異氰酸酯、異氰酸吡啶二基酯等。 Examples of the above-mentioned isocyanate group-containing (meth)acrylate used when introducing the structural unit represented by the above-mentioned general formula (B2) include the molar ratio of hydroxyl-containing (meth)acrylate and diisocyanate compound About 1:1 reaction product. Examples of the hydroxyl-containing (meth)acrylate in the above reaction product include the above-mentioned hydroxyl-containing (meth)acrylate monomers that can be used as the above-mentioned hydroxyl-containing monomers, and hydroxyl-containing polyfunctional ( Meth)acrylate. The hydroxyl-containing polyfunctional (meth)acrylate is a compound having at least one hydroxyl group and two or more (meth)acrylic groups, and is not particularly limited, but preferably has 1 to 4 hydroxyl groups and 2 to 5 A (meth)acrylic acid base. Specific examples of hydroxyl-containing polyfunctional (meth)acrylates include, for example, trimethylolpropane di(meth)acrylate, pentaerythritol bis or tri(meth)acrylate, dipentaerythritol bis, Three, four or five (meth)acrylates, etc. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 3,5,5-isocyanate Trimethyl-3-isocyanatomethylcyclohexyl, meta-or p-xylylene diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, lysine Acid diisocyanate, pyridine diyl isocyanate, etc.

又,上述含異氰酸基之(甲基)丙烯酸酯以相對於上述含羥基之單體之羥基1當量,異氰酸基較佳為0.1當量以上且0.9當量以下,更佳為0.15當量以上且0.8當量以下之方式使用容易使羥值為適當值,就顯影密接性與溶劑再溶解性之方面及著色樹脂組成物之密接性之方面而言較佳。 In addition, the isocyanate group-containing (meth)acrylate is 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the isocyanate group is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more In addition, it is easy to make the hydroxyl value an appropriate value when used in a mode of 0.8 equivalent or less, and it is preferable in terms of development adhesiveness and solvent resolubility, and the adhesiveness of the colored resin composition.

又,上述含異氰酸基之(甲基)丙烯酸酯以相對於上述含羥基之單體之羥基1當量,(甲基)丙烯醯基較佳為0.1當量以上且3.0當量以下,更佳為0.15當量以上且2.5當量以下之方式使用,就亮度及ITO膜之耐龜裂性之方面較佳。 In addition, the isocyanate group-containing (meth)acrylate is 1 equivalent to the hydroxyl group of the hydroxyl-containing monomer, and the (meth)acrylic acid group is preferably 0.1 equivalent or more and 3.0 equivalent or less, more preferably The use of 0.15 equivalent or more and 2.5 equivalent or less is preferable in terms of brightness and crack resistance of the ITO film.

又,於上述通式(B2)所表示之構成單元為使二異氰酸酯化合物之一異氰酸基與源自上述含羥基之單體之構成單元之羥基進行反應,進而使含羥基之(甲基)丙烯酸酯與二異氰酸酯化合物之另一異氰酸基反應而導入之構成單元之情況下,此處之含羥基之(甲基)丙烯酸酯可使用與上述含羥基之(甲基)丙烯酸酯與二異氰酸酯化合物之莫耳比約1:1之反應產物中所說明者相同者。於該情況下,以相對於源自上述含羥基之單體之構成單元之羥基1當量,二異氰酸酯化合物之一異氰酸基較佳為0.1當量以上且0.9當量以下,更佳為0.15當量以上且0.8當量以下之方式使用二異氰酸酯化合物,係容易使羥值為適當值,就顯影密接性與溶劑再溶解性之方面、及著色樹脂組成物之密接性之方面而言較佳。又,較佳為以相對於二異氰酸酯化合物之另一異氰酸基1當量,含羥基之(甲基)丙 烯酸酯之羥基較佳為0.1當量以上且0.9當量以下,更佳為0.15當量以上且0.8當量以下之方式使用含羥基之(甲基)丙烯酸酯。 In addition, the structural unit represented by the above-mentioned general formula (B2) is to react one of the isocyanate groups of the diisocyanate compound with the hydroxyl group derived from the structural unit of the above-mentioned hydroxyl group-containing monomer, thereby making the hydroxyl group-containing (methyl group) ) In the case of a structural unit introduced by reacting another isocyanate group of an acrylate with a diisocyanate compound, the hydroxyl-containing (meth)acrylate here can be used with the above-mentioned hydroxyl-containing (meth)acrylate and The diisocyanate compound has the same molar ratio as the one described in the reaction product of about 1:1. In this case, one of the isocyanate groups of the diisocyanate compound is preferably 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more, based on 1 equivalent of the hydroxyl group of the constituent unit derived from the above-mentioned hydroxyl-containing monomer In addition, the use of the diisocyanate compound in the form of 0.8 equivalents or less makes it easy to make the hydroxyl value an appropriate value, and is preferable in terms of development adhesiveness and solvent resolubility, and adhesiveness of the colored resin composition. Furthermore, it is preferable that the hydroxyl group of the hydroxyl group-containing (meth)acrylate is 0.1 equivalent or more and 0.9 equivalent or less, more preferably 0.15 equivalent or more, based on 1 equivalent of another isocyanate group of the diisocyanate compound. The hydroxyl group-containing (meth)acrylate is used for 0.8 equivalents or less.

於上述嵌段共聚合體中,選自通式(B1)所表示之構成單元及通式(B2)所表示之構成單元中之至少一種之含有比率並無特別限定,相對於嵌段共聚合體之總構成單元之合計質量,較佳為1質量%以上,更佳為3質量%以上,進而更佳為4質量%以上,另一方面,較佳為35質量%以下,更佳為30質量%以下,亦可為20質量%以下。藉由使選自通式(B1)所表示之構成單元及通式(B2)所表示之構成單元中之至少一種之含有比率為上述下限值以上,著色層之亮度、及抑制鄰接於著色層上而形成之ITO膜之龜裂之效果(以下簡稱為ITO膜之耐龜裂性)提高,藉由為上述上限值以下,可提高製版特性。再者,選自通式(B1)所表示之構成單元及通式(B2)所表示之構成單元中之至少一種可為由1種構成者,亦可包含2種以上之構成單元。 In the above-mentioned block copolymer, the content ratio of at least one selected from the constituent unit represented by the general formula (B1) and the constituent unit represented by the general formula (B2) is not particularly limited, and is relative to that of the block copolymer The total mass of the total constituent units is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, on the other hand, it is preferably 35% by mass or less, more preferably 30% by mass Below, it may be 20% by mass or less. By setting the content ratio of at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) to be above the above lower limit, the brightness of the colored layer and the suppression of adjacent coloring The effect of cracking of the ITO film formed on the layer (hereinafter referred to as the crack resistance of the ITO film) is improved, and the plate-making characteristics can be improved by being below the above upper limit. In addition, at least one selected from the structural unit represented by the general formula (B1) and the structural unit represented by the general formula (B2) may be composed of one type, or may include two or more types of structural units.

又,於鹽形成前之嵌段共聚合體中,側鏈所含之(甲基)丙烯醯基當量較佳為100~6000之範圍,尤佳為250~4500之範圍。若該(甲基)丙烯醯基當量為上述下限值以上,則進一步提高著色層之亮度及ITO膜之耐龜裂性,若為上述上限值以下,則提高鹼顯影性、色材分散性、製版特性。此處,所謂(甲基)丙烯醯基當量係指上述鹽形成前之嵌段共聚合體中之(甲基)丙烯醯基每1莫耳之重量平均分子量,以下述數式(1)表示。 In addition, in the block copolymer before salt formation, the equivalent weight of the (meth)acrylic acid group contained in the side chain is preferably in the range of 100 to 6000, particularly preferably in the range of 250 to 4500. If the (meth)acrylic equivalent is more than the above lower limit, the brightness of the colored layer and the crack resistance of the ITO film will be further improved, and if it is below the above upper limit, the alkali developability and color material dispersion will be improved. Performance and plate-making characteristics. Here, the (meth)acryloyl equivalent means the weight average molecular weight of the (meth)acryloyl group per mole in the block copolymer before the salt formation, and is represented by the following formula (1).

數式(1) (甲基)丙烯醯基當量(g/mol)=W'(g)/M'(mol) Numerical formula (1) (meth)acrylic acid equivalent (g/mol)=W'(g)/M'(mol)

(數式(1)中,W'表示鹽形成前之嵌段共聚合體之質量(g),M' 表示鹽形成前之嵌段共聚合體W'(g)中所含之(甲基)丙烯醯基之莫耳數(mol)。) (In the formula (1), W'represents the mass (g) of the block copolymer before the salt is formed, and M'represents the (meth)propylene contained in the block copolymer W'(g) before the salt is formed The number of moles of the base (mol).)

上述(甲基)丙烯醯基當量例如亦可藉由依據JIS K 0070:1992所記載之碘值之試驗方法,測定鹽形成前之嵌段共聚合體每1g中所含之(甲基)丙烯醯基之數量而算出。 The above-mentioned (meth)acrylic acid equivalent weight can also be measured by, for example, the iodine value test method described in JIS K 0070: 1992 to measure the (meth)acrylic acid content per 1 g of the block copolymer before salt formation. Calculated based on the number.

又,於本發明所使用之嵌段共聚合體之合成中,藉由適當調整各構成單元之饋入量,可使嵌段共聚合體所具有之構成單元成為所期望之含有比率,製成具有所期望之性能之共聚合體。其中,於使用上述含羥基之單體與上述含異氰酸基之(甲基)丙烯酸酯導入選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種之情況下,於嵌段共聚合體之合成中,就提高著色層之亮度及ITO膜之耐龜裂性之方面而言,較佳為含羥基之單體之饋入量相對於單體總量為5質量%以上,更佳為10質量%以上。又,就溶劑再溶解性之方面而言,含羥基之單體之饋入量相對於單體總量較佳為50質量%以下,更佳為40質量以下。又,就提高著色層之亮度及ITO膜之耐龜裂性之方面及密接性之方面而言,上述含異氰酸基之(甲基)丙烯酸酯之饋入量相對於上述含羥基之單體之饋入量,較佳為10質量%以上,較佳為15質量%以上,就溶劑再溶解性、顯影密接性、亮度、及ITO膜之耐龜裂性之方面而言,較佳為120質量%以下,更佳為90質量%以下,進而更佳為85質量%以下。 In addition, in the synthesis of the block copolymer used in the present invention, by appropriately adjusting the feeding amount of each constituent unit, the constituent units of the block copolymer can be made to have the desired content ratio, and the Copolymer with desired performance. Among them, the above-mentioned hydroxyl group-containing monomer and the above-mentioned isocyanate group-containing (meth)acrylate are used to introduce the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) In the case of at least one of them, in the synthesis of the block copolymer, in terms of improving the brightness of the colored layer and the crack resistance of the ITO film, it is preferable that the feeding amount of the hydroxyl-containing monomer is relative to The total amount of monomers is 5% by mass or more, more preferably 10% by mass or more. Furthermore, in terms of solvent re-solubility, the feeding amount of the hydroxyl-containing monomer is preferably 50% by mass or less, and more preferably 40% by mass or less with respect to the total amount of monomers. In addition, in terms of improving the brightness of the colored layer and the crack resistance and adhesion of the ITO film, the feeding amount of the isocyanate group-containing (meth)acrylate is relative to the hydroxyl group-containing single The feeding amount of the body is preferably 10% by mass or more, more preferably 15% by mass or more, and in terms of solvent resolubility, development adhesion, brightness, and crack resistance of the ITO film, it is preferably It is 120% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

(其他構成單元) (Other building blocks)

於B嵌段中亦可進而含有提高親溶劑性之其他構成單元。作為 構成B嵌段之上述其他構成單元,可列舉具有能夠與衍生上述通式(I)所表示之構成單元之單體共聚合之不飽和雙鍵之單體,其中較佳為下述通式(II)所表示之構成單元。 The B block may further contain other structural units that improve the solvophilicity. As the above-mentioned other structural unit constituting the B block, a monomer having an unsaturated double bond capable of copolymerizing with the monomer deriving the structural unit represented by the above-mentioned general formula (I) can be mentioned, and among them, the following general formula is preferred (II) The constituent units indicated.

Figure 107106607-A0101-12-0024-11
Figure 107106607-A0101-12-0024-11

(通式(II)中,A'為直接鍵或二價連結基,R4為氫原子或甲基,R5為烴基、-[CH(R6)-CH(R7)-O]x-R8或-[(CH2)y-O]z-R8所表示之一價基;R6及R7分別獨立為氫原子或甲基,R8為氫原子、烴基、-CHO、-CH2CHO、或-CH2COOR9所表示之一價基,R9為氫原子或碳原子數1~5之烷基;上述烴基亦可具有取代基;x表示1~18之整數,y表示1~5之整數,z表示1~18之整數。) (In the general formula (II), A'is a direct bond or a divalent linking group, R 4 is a hydrogen atom or a methyl group, R 5 is a hydrocarbon group, -[CH(R 6 )-CH(R 7 )-O] x -R 8 or -[(CH 2 ) y -O] z -R 8 represents a univalent group; R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, a hydrocarbon group, -CHO, A monovalent group represented by -CH 2 CHO or -CH 2 COOR 9 , R 9 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms; the above-mentioned hydrocarbon group may also have a substituent; x represents an integer of 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)

於通式(II)中,A'為直接鍵或二價連結基。所謂直接鍵係指A'不具有原子,即通式(II)中之C(碳原子)與R5不經由其他原子而鍵結。作為二價連結基,可列舉與通式(I)中之A相同者。作為通式(II)之A',其中就向有機溶劑之溶解性之方面而言,較佳為直接鍵結、亦或是含有-CONH-基或-COO-基之二價連結基。 In the general formula (II), A'is a direct bond or a divalent linking group. The so-called direct bond means that A'does not have atoms, that is, C (carbon atom) and R 5 in the general formula (II) are bonded without other atoms. As a divalent linking group, the same thing as A in general formula (I) can be mentioned. As A'of the general formula (II), in terms of solubility to organic solvents, it is preferably a direct bond or a divalent linking group containing a -CONH- group or a -COO- group.

於通式(II)中,R5表示烴基、-[CH(R6)-CH(R7)-O]x-R8或-[(CH2)y-O]z-R8。作為R5中之烴基,較佳為碳原子數1~18之烷基、碳原子數2~18之烯基、芳烷基、或芳基。上述碳原子數1~18之烷基可為直鏈狀、支鏈狀、環狀之任一者,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、2-乙基己基、2-乙氧基乙基、環戊基、環己基、

Figure 107106607-A0101-12-0024-31
基、異
Figure 107106607-A0101-12-0024-32
基、雙環戊基、二環戊烯基、金剛烷基、 低級烷基取代金剛烷基等。上述碳原子數2~18之烯基可為直鏈狀、支鏈狀、環狀之任一者。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,就所獲得之聚合物之反應性之方面而言,較佳為於烯基之末端具有雙鍵。作為烷基或烯基等脂肪族烴之取代基,可列舉硝基、鹵素原子等。 In the general formula (II), R 5 represents a hydrocarbon group, -[CH(R 6 )-CH(R 7 )-O] x -R 8 or -[(CH 2 ) y -O] z -R 8 . The hydrocarbon group in R 5 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. The above-mentioned alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and 2 -Ethylhexyl, 2-ethoxyethyl, cyclopentyl, cyclohexyl,
Figure 107106607-A0101-12-0024-31
Base, different
Figure 107106607-A0101-12-0024-32
Group, dicyclopentyl, dicyclopentenyl, adamantyl, lower alkyl substituted adamantyl, etc. The above-mentioned alkenyl group having 2 to 18 carbon atoms may be linear, branched, and 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. In terms of the reactivity of the obtained polymer, it is preferable to have a double bond at the end of the alkenyl group. Examples of the substituent of aliphatic hydrocarbons such as an alkyl group or an alkenyl group include a nitro group and a halogen atom.

作為芳基,可列舉苯基、聯苯基、萘基、甲苯基、二甲苯基等,亦可進而具有取代基。芳基之碳原子數較佳為6~24,進而較佳為6~12。又,作為芳烷基,可列舉苄基、苯乙基、萘基甲基、聯苯甲基等,亦可進而具有取代基。芳烷基之碳原子數較佳為7~20,進而較佳為7~14。作為芳基或芳烷基等芳香環之取代基,除碳原子數1~4之直鏈狀、支鏈狀之烷基以外,可列舉烯基、硝基、鹵素原子等。再者,上述較佳之碳原子數不包含取代基之碳原子數。 As an aryl group, a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aryl group is preferably 6-24, and more preferably 6-12. Moreover, as an aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, etc. are mentioned, and it may have a substituent further. The number of carbon atoms of the aralkyl group is preferably 7-20, and more preferably 7-14. As the substituent of the aromatic ring such as an aryl group or an aralkyl group, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms, an alkenyl group, a nitro group, a halogen atom, etc. can be mentioned. Furthermore, the above-mentioned preferred number of carbon atoms does not include the number of carbon atoms of the substituent.

於上述R5中,x為1~18之整數,較佳為1~4之整數,更佳為1~2之整數,y為1~5之整數,較佳為1~4之整數,更佳為2或3。z為1~18之整數,較佳為1~4之整數,更佳為1~2之整數。 In the above R 5 , x is an integer from 1 to 18, preferably an integer from 1 to 4, more preferably an integer from 1 to 2, and y is an integer from 1 to 5, preferably an integer from 1 to 4, and more Preferably it is 2 or 3. z is an integer of 1-18, preferably an integer of 1-4, more preferably an integer of 1-2.

上述R8中之烴基設為與上述R5中所示者相同者。R9亦可為氫原子或碳原子數1~5之烷基且為直鏈狀、支鏈狀、或環狀之任一者。又,上述通式(II)所表示之構成單元中之R5可相互相同,亦可不同。 The hydrocarbon group in the above R 8 is the same as that shown in the above R 5. R 9 may be a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be any of linear, branched, or cyclic. In addition, R 5 in the structural unit represented by the general formula (II) may be the same as or different from each other.

作為上述R5,其中較佳為以成為與下述溶劑之相溶性優異者之方式選定,具體而言,例如於上述溶劑使用通常用作彩色濾光片用著色樹脂組成物之溶劑之二醇醚乙酸酯系、醚系、酯系 等溶劑之情況下,較佳為甲基、乙基、異丁基、正丁基、2-乙基己基、苄基等。 Among them, R 5 is preferably selected so as to have excellent compatibility with the following solvents. Specifically, for example, a diol that is generally used as a solvent for the colored resin composition for color filters is used for the above-mentioned solvent. In the case of solvents such as ether acetate-based, ether-based, and ester-based solvents, methyl, ethyl, isobutyl, n-butyl, 2-ethylhexyl, benzyl, etc. are preferred.

進而,上述R5亦可設為於不妨礙上述嵌段共聚合體之分散性能等之範圍內經烷氧基、羥基、酸性基、環氧基、異氰酸基等取代基取代者,又,亦可於上述嵌段共聚合體之合成後,使其與具有上述取代基之化合物進行反應而加成上述取代基。 Furthermore, the above R 5 may be substituted with a substituent such as an alkoxy group, a hydroxyl group, an acidic group, an epoxy group, an isocyanate group, etc. within a range that does not hinder the dispersibility of the block copolymer, etc., and also, After the above-mentioned block copolymer is synthesized, it can be reacted with the compound having the above-mentioned substituent to add the above-mentioned substituent.

(源自含酸性基之單體之構成單元) (Constituted units derived from monomers containing acidic groups)

就提高B嵌段之親溶劑性且提高色材分散液之分散性及分散穩定性之方面而言,較佳為B嵌段進而包含源自含酸性基之單體之構成單元。作為上述含酸性基之單體,例如可列舉含有能夠與衍生通式(I)所表示之構成單元之單體共聚合之不飽和雙鍵與酸性基之單體。作為上述酸性基,例如可列舉羧基、磷酸基、磺基、硼酸基等,其中就顯影性之方面而言,較佳為羧基。作為含羧基單體,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、衣康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基之單體與如順丁烯二酸酐或酞酸酐、環己烷二羧酸酐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、衣康酸酐、檸康酸酐等含酸酐基之單體作為羧基之前驅物。其中,就共聚合性或成本、溶解性、玻璃轉移溫度等方面而言,尤佳為(甲基)丙烯酸。 In terms of improving the solvent affinity of the B block and improving the dispersibility and dispersion stability of the color material dispersion liquid, it is preferable that the B block further contains a structural unit derived from an acidic group-containing monomer. As the above-mentioned acidic group-containing monomer, for example, a monomer containing an unsaturated double bond and an acidic group which can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) is mentioned. As said acidic group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a boronic acid group, etc. are mentioned, for example, Among them, a carboxyl group is preferable in terms of developability. Examples of carboxyl group-containing monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, itaconic acid, and crotonic acid. , Cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, monomers containing acid anhydride groups, such as maleic anhydride, itaconic anhydride, and citraconic acid anhydride, may also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

於含有源自含酸性基之單體之構成單元的情況下,於鹽形成前之嵌段共聚合體中,源自含酸性基之單體之構成單元的含 有比率並無特別限定,相對於嵌段共聚合體之總構成單元之合計質量,較佳為0.05~4.5質量%,更佳為0.07~3.7質量%。藉由使源自含酸性基之單體之構成單元的含有比率為上述下限值以上,顯影殘渣之抑制效果優異,藉由為上述上限值以下,可防止顯影密接性之劣化或溶劑再溶解性之劣化。再者,源自含酸性基之單體之構成單元可為由1種所構成者,亦可包含2種以上之構成單元。 In the case of containing the structural unit derived from the acidic group-containing monomer, the content ratio of the structural unit derived from the acidic group-containing monomer in the block copolymer before salt formation is not particularly limited. The total mass of the total constituent units of the stage copolymer is preferably 0.05 to 4.5% by mass, more preferably 0.07 to 3.7% by mass. By setting the content ratio of the structural unit derived from the acidic group-containing monomer to be above the above lower limit, the effect of suppressing development residues is excellent, and by being below the above upper limit, it is possible to prevent deterioration of development adhesion or resolving Deterioration of solubility. In addition, the structural unit derived from the acidic group-containing monomer may be composed of one type, or may include two or more types of structural units.

構成B嵌段之構成單元之數量並無特別限定,就親溶劑性部位與親色材部位有效地發揮作用,提高色材之分散性之方面而言,較佳為10~300個,更佳為10~100個,進而更佳為10~70個。 The number of structural units constituting the B block is not particularly limited. In terms of the solvent-philic part and the color-philic material part effectively functioning to improve the dispersibility of the color material, it is preferably 10 to 300, and more preferably It is 10 to 100 pieces, and more preferably 10 to 70 pieces.

於嵌段共聚合體中之B嵌段中,上述通式(II)所表示之構成單元之含有比率就提高親溶劑性或色材分散性之方面而言,相對於B嵌段之總構成單元之合計質量,較佳為30~95質量%,更佳為40~90質量%。再者,上述構成單元之含有比率係由合成B嵌段時之饋入質量算出。 In the B block in the block copolymer, the content ratio of the structural unit represented by the above general formula (II) is relative to the total structural unit of the B block in terms of improving the solubility of the solvent and the dispersibility of the color material. The total mass is preferably 30-95% by mass, more preferably 40-90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when synthesizing the B block.

又,於鹽形成前之嵌段共聚合體中,上述通式(II)所表示之構成單元之含有比率就提高色材分散性之方面而言,相對於嵌段共聚合體之總構成單元之合計質量,較佳為40~95質量%,更佳為50~90質量%。再者,上述構成單元之含有比率係由合成鹽形成前之嵌段共聚合體時之饋入質量算出。 In addition, in the block copolymer before salt formation, the content ratio of the structural unit represented by the above general formula (II) is relative to the total of the total structural units of the block copolymer in terms of improving the dispersibility of the color material The mass is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when the block copolymer before the formation of the salt is synthesized.

B嵌段較佳為以作為親溶劑性部位發揮功能之方式適當選擇構成單元,上述通式(II)所表示之構成單元可為由1種所構成者,亦可包含2種以上之構成單元。B嵌段中所含之2種以上之構成單元亦可於該嵌段內無規地排列。 The B block is preferably a constitutional unit appropriately selected so as to function as a solvophilic site. The constitutional unit represented by the above general formula (II) may be composed of one type or two or more types of constitutional units. . Two or more structural units contained in the B block may be randomly arranged in the block.

於本發明中,就提高顯影密接性之方面而言,較佳為於鹽形成前之嵌段共聚合體之B嵌段中包含源自上述含羥基之單體之構成單元。於包含源自上述含羥基之單體之構成單元之情況下,認為容易與通常用作基板之玻璃或金屬等相互作用,因此顯影密接性提高。於B嵌段中包含源自上述含羥基之單體之構成單元之情況下,顯影速度亦進一步提高。 In the present invention, it is preferable that the B block of the block copolymer before the salt formation includes a structural unit derived from the above-mentioned hydroxyl group-containing monomer in terms of improving the adhesiveness of development. In the case of containing the structural unit derived from the above-mentioned hydroxyl-containing monomer, it is considered that it is likely to interact with glass or metal that is generally used as a substrate, and therefore the development adhesion is improved. When the B block contains the structural unit derived from the above-mentioned hydroxyl group-containing monomer, the development speed is further improved.

於含有源自含羥基之單體之構成單元之情況下,於鹽形成前之嵌段共聚合體中,源自含羥基之單體之構成單元之含有比率相對於嵌段共聚合體之總構成單元之合計質量,較佳為1質量%以上,更佳為2質量%以上,進而更佳為3質量%以上,尤佳為4質量%以上。若為上述下限值以上,則可成為顯影密接性較佳者。同樣地,較佳為70質量%以下,更佳為60質量%以下,進而更佳為50質量%以下,尤佳為40質量%以下。若為上述上限值以下,則可成為就提高其他有用之單體之導入比率的方面而言較佳者。再者,上述構成單元之含有比率係由合成鹽形成前之嵌段共聚合體時之饋入質量算出。 In the case of containing structural units derived from hydroxyl-containing monomers, the ratio of the content of structural units derived from hydroxyl-containing monomers to the total structural units of the block copolymer in the block copolymer before salt formation The total mass of the bismuth is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. If it is more than the said lower limit, it can become a thing with better development adhesiveness. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is less than the above upper limit, it can be preferable in terms of increasing the introduction ratio of other useful monomers. In addition, the content ratio of the above-mentioned structural unit is calculated from the feed mass when the block copolymer before the formation of the salt is synthesized.

又,於本發明中,就提高溶劑再溶解性之方面而言,較佳為於B嵌段中包含源自含芳香族基之單體之構成單元。於包含源自含芳香族基之單體之構成單元的情況下,認為容易提高與溶劑或其他成分之相溶性,因此提高溶劑再溶解性。作為源自含芳香族基之單體之構成單元,可使用含有能夠與衍生通式(I)所表示之構成單元之單體共聚合之不飽和雙鍵與芳香族基之單體。作為此種單體,例如可列舉:(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸苯氧基乙酯等丙烯酸酯類、苯乙烯等苯乙烯 類、苯基乙烯醚等乙烯醚類。就提高顯影密接性之方面而言,其中,較佳為使用各單體之均聚物之玻璃轉移溫度之值(Tgi)成為0℃以上之含芳香族基之單體,進而較佳為使用成為10℃以上之含芳香族基之單體。就容易提高再溶解性之方面而言,其中,較佳為選自由(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、及(甲基)丙烯酸苯氧基乙酯所構成之群中之1種以上,進而較佳為選自由(甲基)丙烯酸苄酯、及(甲基)丙烯酸2-羥基-3-苯氧基丙酯所構成之群中之1種以上。 Furthermore, in the present invention, it is preferable to include a structural unit derived from an aromatic group-containing monomer in the B block in terms of improving solvent resolubility. In the case of containing the structural unit derived from the aromatic group-containing monomer, it is considered that the compatibility with the solvent or other components is easily improved, and therefore the solvent resolubility is improved. As the structural unit derived from the aromatic group-containing monomer, a monomer containing an unsaturated double bond and an aromatic group that can be copolymerized with the monomer that derives the structural unit represented by the general formula (I) can be used. Examples of such monomers include acrylic esters such as benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and phenoxyethyl (meth)acrylate, Styrenes such as styrene, vinyl ethers such as phenyl vinyl ether. In terms of improving the development adhesion, among them, it is preferable to use the value of the glass transition temperature (Tgi) of the homopolymer of each monomer to be 0°C or higher and the aromatic group-containing monomer is more preferable to use Becomes an aromatic group-containing monomer above 10°C. In terms of easy improvement of resolubility, among them, it is preferably selected from the group consisting of benzyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and benzene (meth)acrylate One or more of the group consisting of oxyethyl ester, more preferably selected from the group consisting of benzyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate One or more of them.

於含有源自含芳香族基之單體之構成單元的情況下,就提高溶劑再溶解性之方面而言,於鹽形成前之嵌段共聚合體中,源自含芳香族基之單體之構成單元之含有比率相對於嵌段共聚合體之總構成單元之合計質量,較佳為1質量%以上,更佳為2質量%以上,進而更佳為3質量%以上,尤佳為4質量%以上。若為上述下限值以上,則可成為溶劑再溶解性較佳者。同樣地,較佳為70質量%以下,更佳為60質量%以下,進而更佳為50質量%以下,尤佳為40質量%以下。若為上述上限值以下,則可成為就提高其他有用之單體之導入比率之方面而言較佳者。 In the case of containing structural units derived from aromatic group-containing monomers, in terms of improving solvent re-solubility, in the block copolymer before salt formation, it is derived from aromatic group-containing monomers. The content ratio of the constituent units relative to the total mass of the total constituent units of the block copolymer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass the above. If it is more than the above-mentioned lower limit, it can become the one with better solvent resolubility. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is less than the above upper limit, it can be preferable in terms of increasing the introduction ratio of other useful monomers.

又,其中,就提高顯影密接性及溶劑再溶解性之方面而言,較佳為B嵌段包含(i)源自含羥基之單體之構成單元及源自含芳香族基之單體之構成單元、以及(ii)源自含羥基及芳香族基之單體之構成單元之至少一種。 Furthermore, among them, in terms of improving development adhesion and solvent re-solubility, it is preferable that the B block contains (i) a constituent unit derived from a hydroxyl-containing monomer and a monomer derived from an aromatic group-containing monomer. The structural unit and (ii) at least one of structural units derived from a monomer containing a hydroxyl group and an aromatic group.

於分別包含(i)源自含羥基之單體之構成單元及源自含芳香族基之單體之構成單元之情況下,相對於源自含芳香族基之單體之構成單元1質量份,較佳為含有源自含羥基之單體之構成單 元0.15質量份以上,進而較佳為含有0.5質量份以上。其原因在於,若為上述下限值以上,則可成為顯影密接性優異者。又,同樣地,相對於含芳香族基之單體之構成單元1質量份,較佳為以15質量份以下含有源自含羥基之單體之構成單元,進而較佳為以7質量份以下含有源自含羥基之單體之構成單元。其原因在於,若為上述上限值以下,則可成為溶劑再溶解性優異者。其中,相對於均聚物之玻璃轉移溫度之值(Tgi)成為10℃以上之源自含芳香族基之單體之構成單元1質量份,尤佳為以上述範圍含有均聚物之玻璃轉移溫度之值(Tgi)成為10℃以上之源自含羥基之單體之構成單元。其原因在於,藉由以上述下限值以上含有,可使顯影密接性更優異,藉由以上述上限值以下含有,可使溶劑再溶解性更優異。 When (i) a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from an aromatic group-containing monomer are included, relative to 1 part by mass of a structural unit derived from an aromatic group-containing monomer It is preferable to contain 0.15 parts by mass or more of structural units derived from a hydroxyl-containing monomer, and more preferably to contain 0.5 parts by mass or more. The reason is that if it is equal to or more than the above lower limit value, it can be excellent in development adhesiveness. Also, similarly, it is preferable to contain the structural unit derived from the hydroxyl-containing monomer in 15 parts by mass or less with respect to 1 part by mass of the structural unit of the aromatic group-containing monomer, and more preferably 7 parts by mass or less Contains structural units derived from hydroxyl-containing monomers. The reason is that if it is not more than the above upper limit value, it can be excellent in solvent resolubility. Among them, the value of the glass transition temperature (Tgi) relative to the homopolymer is 1 part by mass of the structural unit derived from the aromatic group-containing monomer at 10°C or higher, and the glass transition containing the homopolymer in the above range is particularly preferred. The value of temperature (Tgi) becomes a structural unit derived from a hydroxyl-containing monomer above 10°C. The reason is that by containing at least the above lower limit value, the development adhesiveness can be made more excellent, and by containing at the above upper limit value or less, the solvent resolubility can be made more excellent.

又,作為(ii)源自含羥基及芳香族基之單體之構成單元中之含羥基及芳香族基之單體,例如可列舉:(甲基)丙烯酸2-羥基-3-苯氧基丙酯、2-丙烯醯氧基乙基-2-羥基乙基-酞酸等。就均聚物之玻璃轉移溫度之值(Tgi)為10℃以上,且可獲得由源自含羥基之單體之構成單元所獲得之效果與由源自含芳香族基之單體之構成單元所獲得之效果兩者之方面而言,較佳為使用(甲基)丙烯酸2-羥基-3-苯氧基丙酯。即,其原因在於,於提高顯影密接性、顯影速度、溶劑再溶解性之方面較佳。於包含(ii)源自含羥基及芳香族基之單體之構成單元之情況下,可藉由一個構成單元而提高顯影密接性、顯影速度、溶劑再溶解性,因此亦有可提高其他功能性單體之導入比率之優點。 In addition, examples of (ii) monomers containing a hydroxyl group and an aromatic group in the structural unit derived from a monomer containing a hydroxyl group and an aromatic group include: (meth)acrylic acid 2-hydroxy-3-phenoxy group Propyl ester, 2-propenyloxyethyl-2-hydroxyethyl-phthalic acid and the like. The value of the glass transition temperature (Tgi) of the homopolymer is 10°C or more, and the effect obtained by the structural unit derived from the hydroxyl-containing monomer and the structural unit derived from the aromatic group-containing monomer can be obtained In terms of both the effects obtained, it is preferable to use 2-hydroxy-3-phenoxypropyl (meth)acrylate. That is, the reason is that it is preferable in terms of improvement in development adhesion, development speed, and solvent resolubility. In the case of containing (ii) a structural unit derived from a monomer containing a hydroxyl group and an aromatic group, a single structural unit can improve development adhesion, development speed, and solvent resolubility, so other functions can also be improved Advantages of the introduction ratio of sexual monomers.

又,就提高顯影密接性之方面而言,較佳為使單體之均聚物之玻璃轉移溫度之值(Tgi)為10℃以上之單體合計於B嵌段 中為75質量%以上,進而較佳為85質量%以上。 Also, in terms of improving the development adhesion, it is preferable to make the value (Tgi) of the glass transition temperature (Tgi) of the homopolymer of the monomers of 10°C or more in the total of the monomers in the B block 75% by mass or more, More preferably, it is 85% by mass or more.

於上述嵌段共聚合體中,作為上述A嵌段之構成單元之單元數m與上述B嵌段之構成單元之單元數n之比率m/n,較佳為0.05~1.5之範圍內,就色材分散性、分散穩定性之方面而言,更佳為0.1~1.0之範圍內。 In the above-mentioned block copolymer, the ratio m/n of the unit number m of the structural unit of the A block to the unit number n of the structural unit of the B block is preferably in the range of 0.05 to 1.5. In terms of material dispersibility and dispersion stability, it is more preferably in the range of 0.1 to 1.0.

又,鹽形成前之嵌段共聚合體之胺值並無特別限定,就色材分散性及分散穩定性之方面而言,作為下限,較佳為40mgKOH/g以上,更佳為50mgKOH/g以上,進而更佳為60mgKOH/g以上。又,作為上限,較佳為140mgKOH/g以下,更佳為130mgKOH/g以下,進而更佳為120mgKOH/g以下。若為上述下限值以上,則分散穩定性更優異。又,若為上述上限值以下,則與其他成分之相溶性優異,溶劑再溶解性變得良好。再者,本發明中,所謂鹽形成前之嵌段共聚合體之胺值,係表示為相對於中和鹽形成前之嵌段共聚合體之固形物成分1g所需要之鹽酸量,以當量表示之氫氧化鉀之質量(mg),且係藉由JIS K 7237:1995所記載之方法而測得之值。 In addition, the amine value of the block copolymer before salt formation is not particularly limited. In terms of color material dispersibility and dispersion stability, the lower limit is preferably 40 mgKOH/g or more, more preferably 50 mgKOH/g or more , And more preferably 60 mgKOH/g or more. Moreover, as an upper limit, 140 mgKOH/g or less is preferable, 130 mgKOH/g or less is more preferable, and 120 mgKOH/g or less is still more preferable. If it is more than the above lower limit, the dispersion stability is more excellent. Moreover, if it is less than the said upper limit, the compatibility with other components will be excellent, and the solvent re-solubility will become favorable. Furthermore, in the present invention, the so-called amine value of the block copolymer before salt formation is expressed as the amount of hydrochloric acid required for 1 g of the solid content of the block copolymer before salt formation, expressed in equivalents The mass (mg) of potassium hydroxide is a value measured by the method described in JIS K 7237:1995.

上述嵌段共聚合體之重量平均分子量Mw並無特別限定,就使色材分散性及分散穩定性良好之方面而言,較佳為1000~20000,更佳為2000~15000,進而更佳為3000~12000。此處,重量平均分子量(Mw)係藉由凝膠滲透層析法(GPC),作為標準聚苯乙烯換算值而求出。再者,本發明中,嵌段共聚合體之重量平均分子量Mw係藉由GPC(凝膠滲透層析法),作為標準聚苯乙烯換算值而求出。測定係使用Tosoh股份有限公司製造之HLC-8120GPC,將溶出溶劑設為添加有0.01莫耳/升之溴化鋰之N-甲基吡咯啶酮, 將校正曲線用聚苯乙烯標準設為Mw377400、210500、96000、50400、20650、10850、5460、2930、1300、580(以上為Polymer Laboratories公司製造,Easi PS-2系列)及Mw1090000(Tosoh股份有限公司製造),將測定管柱設為TSK-GEL ALPHA-M×2根(Tosoh股份有限公司製造)而進行。再者,關於成為嵌段共聚合體之原料之巨單體或鹽型嵌段共聚合體、接枝共聚合體,亦於上述條件下進行。 The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, but it is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 3,000 in terms of good color material dispersibility and dispersion stability. ~12000. Here, the weight average molecular weight (Mw) is calculated as a standard polystyrene conversion value by gel permeation chromatography (GPC). In addition, in the present invention, the weight average molecular weight Mw of the block copolymer is determined as a standard polystyrene conversion value by GPC (gel permeation chromatography). The measurement system uses HLC-8120GPC manufactured by Tosoh Co., Ltd., the dissolution solvent is N-methylpyrrolidone added with 0.01 mol/L lithium bromide, and the polystyrene standard for the calibration curve is set to Mw377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (the above are made by Polymer Laboratories, Easi PS-2 series) and Mw1090000 (made by Tosoh Co., Ltd.), set the measuring column to TSK-GEL ALPHA- M×2 (manufactured by Tosoh Co., Ltd.). Furthermore, the macromonomers, salt-type block copolymers, and graft copolymers used as raw materials for the block copolymers are also carried out under the above-mentioned conditions.

本發明中,嵌段共聚合體之各嵌段之配置並無特別限定,例如可設為AB嵌段共聚合體、ABA嵌段共聚合體、BAB嵌段共聚合體等。其中,就分散性優異之方面而言,較佳為AB嵌段共聚合體、或ABA嵌段共聚合體。 In the present invention, the arrangement of each block of the block copolymer is not particularly limited. For example, it may be an AB block copolymer, an ABA block copolymer, a BAB block copolymer, and the like. Among them, in terms of excellent dispersibility, AB block copolymers or ABA block copolymers are preferred.

上述嵌段共聚合體之製造方法並無特別限定。可藉由公知方法製造嵌段共聚合體,其中,較佳為藉由活性聚合法進行製造。其原因在於,可製造出不易產生鏈轉移或失活而分子量一致之共聚合體,可提高分散性等。作為活性聚合法,可列舉活性自由基聚合法、基轉移聚合法等活性陰離子聚合法、活性陽離子聚合法等。可藉由利用該等方法使單體依序聚合而製造共聚合體。例如可藉由先製造A嵌段,使構成B嵌段之構成單元與A嵌段聚合而製造嵌段共聚合體。又,於上述製造方法中,亦可使A嵌段與B嵌段之聚合之順序相反。又,亦可分別製造A嵌段與B嵌段,其後使A嵌段與B嵌段偶合。 The manufacturing method of the said block copolymer is not specifically limited. The block copolymer can be produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason is that it is possible to produce copolymers with uniform molecular weights that are not prone to chain transfer or deactivation, and to improve dispersibility and the like. Examples of the living polymerization method include living anionic polymerization methods such as living radical polymerization methods and radical transfer polymerization methods, living cationic polymerization methods, and the like. Copolymers can be produced by sequentially polymerizing monomers using these methods. For example, a block copolymer can be produced by first producing the A block and polymerizing the constituent units constituting the B block with the A block. In addition, in the above-mentioned production method, the order of polymerization of the A block and the B block may be reversed. In addition, the A block and the B block may be produced separately, and then the A block and the B block may be coupled.

{選自由有機酸化合物及鹵代烴所構成之群中之至少一種} {At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons}

本發明中,作為上述嵌段共聚合體,就提高色材分散性之方面 而言,較佳為上述通式(I)所表示之構成單元之末端之氮部位之至少一部分,與選自由有機酸化合物及鹵代烴所構成之群中之至少一種形成鹽之鹽型嵌段共聚合體。作為上述有機酸化合物,其中較佳為下述通式(1)所表示之化合物及下述通式(3)所表示之化合物,作為上述鹵代烴,其中較佳為下述通式(2)所表示之化合物。即,作為選自由上述有機酸化合物及鹵代烴所構成之群中之至少一種,較佳可使用選自由下述通式(1)~(3)所構成之群中之1種以上之化合物。 In the present invention, the block copolymer is preferably at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) in terms of improving the dispersibility of the color material, and is selected from organic acids At least one of the group consisting of the compound and the halogenated hydrocarbon forms a salt-type block copolymer of a salt. As the above-mentioned organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferred, and as the above-mentioned halogenated hydrocarbon, among them, the following general formula (2) is preferred. ) Represented by the compound. That is, as at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons, preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3) can be used .

Figure 107106607-A0101-12-0033-12
Figure 107106607-A0101-12-0033-12

(於通式(1)中,Ra表示碳數1~20之直鏈、支鏈或環狀之烷基、乙烯基、可具有取代基之苯基或苄基、或-O-Re,Re表示碳數1~20之直鏈、支鏈或環狀之烷基、乙烯基、可具有取代基之苯基或苄基、或介隔有碳數1~4之伸烷基的(甲基)丙烯醯基;於通式(2)中,Rb、Rb'及Rb"分別獨立地表示氫原子、酸性基或其酯基、可具有取代基之碳數1~20之直鏈、支鏈或環狀之烷基、可具有取代基之乙烯基、可具有取代基之苯基或苄基、或-O-Rf,Rf表示可具有取代基之碳數1~20直鏈、支鏈或環狀之烷基、可具有取代基之乙烯基、可具有取代基之苯基或苄基、或介隔碳數1~4之伸烷基之(甲基)丙烯醯基,X表示氯原子、溴原子或碘原子;於通式(3)中,Rc及Rd分別獨立地表示氫原子、羥基、碳數1~20之直鏈、支鏈或環狀之烷基、乙烯基、可具有取代基之苯基或苄基、或-O-Re,Re表示碳數1~20之直鏈、支鏈或環狀之烷基、乙烯基、可具有取代基之苯基或苄基、 或介隔碳數1~4之伸烷基之(甲基)丙烯醯基;其中,Rc及Rd之至少一個包含碳原子。) (In the general formula (1), R a represents a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms, a vinyl group, a substituted phenyl group or a benzyl group, or -OR e , R e represents a linear, branched or cyclic alkyl group with 1 to 20 carbons, a vinyl group, a phenyl group or a benzyl group which may have a substituent, or an alkylene group with a carbon number of 1 to 4 (former yl) Bingxi Xi group; in formula 2) (, R b, R b 'and R b "each independently represent a hydrogen atom, an acidic group or an ester thereof, may have a substituent group of carbon number 1 to 20 of a linear Chain, branched or cyclic alkyl group, optionally substituted vinyl group, optionally substituted phenyl or benzyl group, or -OR f , R f represents optionally substituted carbon number 1-20 straight chain , Branched or cyclic alkyl group, optionally substituted vinyl group, optionally substituted phenyl or benzyl group, or (meth)acryloyl group with an alkylene having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom or an iodine atom; in the general formula (3), R c and Rd each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms , Vinyl, phenyl or benzyl which may have substituents, or -OR e , R e represents linear, branched or cyclic alkyl with 1 to 20 carbons, vinyl, benzene which may have substituents (Meth)acryloyl group or benzyl group, or a (meth)acryloyl group with an alkylene having 1 to 4 carbon atoms; wherein at least one of R c and R d contains a carbon atom.)

(選自由上述通式(1)~(3)所構成之群中之1種以上之化合物) (Selected from one or more compounds from the group consisting of the above general formulas (1) to (3))

於上述通式(1)~(3)中,作為Ra、Rb、Rb'、Rb"、Rc、Rd、Re及Rf中之碳數1~20之直鏈、支鏈或環狀之烷基,可為直鏈或支鏈之任一者,又,亦可包含環狀構造,具體而言,可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、十二烷基、環戊基、環己基、十四烷基、十八烷基等。較佳可列舉碳數1~15之直鏈、支鏈或環狀之烷基,進而較佳可列舉碳數1~8之直鏈、支鏈或環狀之烷基。又,於Ra、Rc、Rd及Re中,作為可具有取代基之苯基或苄基之取代基,例如可列舉碳原子數為1~5之烷基、醯基、醯氧基等。 In the general formula (1) to (3), as R a, R b, R b ', R b ", R c, R d, R e , and the carbon atoms in R f is a straight chain of 1 to 20, The branched or cyclic alkyl group may be either linear or branched, and may also include a cyclic structure. Specifically, examples include methyl, ethyl, n-propyl, and isopropyl , N-butyl, isobutyl, second butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, twelve Alkyl, cyclopentyl, cyclohexyl, tetradecyl, octadecyl, etc. Preferably, straight, branched or cyclic alkyl groups with 1 to 15 carbon atoms can be cited, and more preferably, the number of carbon atoms can be cited 1 to 8 of a linear, branched or cyclic alkyl group of. Furthermore, in R a, R c, R d and R e, the group as a substituent of a phenyl or benzyl substituent of the group, include e.g. Alkyl groups, acyl groups, acyloxy groups, etc. having 1 to 5 carbon atoms.

於Rb、Rb'、Rb"及Rf中,作為可具有取代基之苯基或苄基之取代基,例如可列舉酸性基或其酯基、碳原子數為1~5之烷基、醯基、醯氧基等。又,於Rb、Rb'、Rb"及Rf中,作為可具有取代基之碳數1~20之直鏈、支鏈或環狀之烷基、或乙烯基之取代基,可列舉酸性基或其酯基、苯基、醯基、醯氧基等。於Rb、Rb'、Rb"及Rf中,所謂酸性基係指於水中釋出質子而顯示酸性之基。作為酸性基之具體例,可列舉羧基(-COOH)、磺基(-SO3H)、膦酸基(-P(=O)(OH)2)、膦酸亞基(>P(=O)(OH))、

Figure 107106607-A0101-12-0034-33
酸基(-B(OH)2)、二取代硼酸基(>BOH)等,亦可為如羧酸酯基(-COO-)等般氫原子解離之陰離子,進而亦可為與鈉離子或鉀離子等鹼金屬離子形成鹽之酸性 鹽。又,作為酸性基之酯基,可列舉羧酸酯(-COOR)、磺酸酯(-SO3R)、磷酸酯(-P(=O)(OR)2)、(>P(=O)(OR))、
Figure 107106607-A0101-12-0035-34
酸酯(-B(OR)2)、二取代硼酸酯(>BOR)等。其中,作為酸性基之酯基,就分散性及分散穩定性之方面而言,較佳為羧酸酯(-COOR)。再者,R為烴基,並無特別限定,就分散性及分散穩定性之方面而言,其中較佳為碳原子數1~5之烷基,更佳為甲基或乙基。 In R b , R b' , R b" and R f , as the substituent of the optionally substituted phenyl or benzyl group, for example, an acidic group or an ester group thereof, and an alkane having 1 to 5 carbon atoms can be mentioned. Group, acyl group, acyloxy group, etc. In addition, in R b , R b' , R b" and R f , it is used as a linear, branched or cyclic alkane with 1 to 20 carbon atoms that may have a substituent The substituent of the group or the vinyl group includes an acidic group or its ester group, a phenyl group, an acyl group, and an acyloxy group. In R b , R b' , R b" and R f , the so-called acidic group refers to a group that releases protons in water to show acidity. Specific examples of acidic groups include carboxyl (-COOH), sulfo ( -SO 3 H), phosphonic acid group (-P(=O)(OH) 2 ), phosphonic acid subunit (>P(=O)(OH)),
Figure 107106607-A0101-12-0034-33
Acid groups (-B(OH) 2 ), di-substituted boronic acid groups (>BOH), etc., can also be anions that dissociate hydrogen atoms such as carboxylate groups (-COO-), and can also be anions with sodium ions or Alkali metal ions such as potassium ion form acid salt of salt. In addition, as the ester group of the acidic group, carboxylate (-COOR), sulfonate (-SO 3 R), phosphate (-P(=O)(OR) 2 ), (>P(=O) )(OR)),
Figure 107106607-A0101-12-0035-34
Ester (-B(OR) 2 ), disubstituted borate (>BOR), etc. Among them, the ester group as an acidic group is preferably a carboxylic acid ester (-COOR) in terms of dispersibility and dispersion stability. Furthermore, R is a hydrocarbon group and is not particularly limited. In terms of dispersibility and dispersion stability, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.

就分散性、分散穩定性、鹼顯影性及抑制顯影殘渣之方面而言,上述通式(2)之化合物較佳為具有選自羧基、

Figure 107106607-A0101-12-0035-35
酸基、二取代硼酸基、該等之陰離子以及該等之鹼金屬鹽、及該等之酯中之1種以上之官能基,其中更佳為具有選自羧基、羧酸酯基、羧酸鹽基及羧酸酯中之官能基。於上述通式(2)之化合物具有酸性基及其酯基(以下稱為酸性基等)之情況下,推斷該化合物所具有之酸性基等側及鹵素原子側烴均可與末端之氮部位形成鹽,但相較末端之氮部位與酸性基等形成鹽之情況,末端之氮部位與鹵素原子側烴穩定地形成鹽。而且,推斷藉由使色材吸附至穩定地存在之鹽形成部位,分散性及分散穩定性提高。 In terms of dispersibility, dispersion stability, alkali developability and suppression of development residues, the compound of the above general formula (2) preferably has a carboxyl group,
Figure 107106607-A0101-12-0035-35
One or more functional groups among acid groups, disubstituted boronic acid groups, these anions, alkali metal salts, and these esters, and more preferably have one selected from the group consisting of carboxyl, carboxylate, and carboxylic acid The functional group in the base and carboxylate. In the case where the compound of the above general formula (2) has an acidic group and its ester group (hereinafter referred to as acidic group, etc.), it is inferred that the acidic group and other side and halogen atom side hydrocarbons that the compound has can interact with the terminal nitrogen site A salt is formed, but compared to the case where the terminal nitrogen site forms a salt with an acidic group, the terminal nitrogen site and the halogen atom side hydrocarbon stably form a salt. Furthermore, it is inferred that the dispersibility and dispersion stability are improved by adsorbing the color material to the stably existing salt formation site.

於上述通式(2)之化合物具有上述酸性基等之情況下,亦可具有2個以上之上述酸性基等。於具有2個以上之上述酸性基等之情況下,具有數個之上述酸性基等可相同,亦可不同。上述通式(2)之化合物所具有之上述酸性基等之數量較佳為1~3個,更佳為1~2個,進而更佳為1個。 When the compound of the aforementioned general formula (2) has the aforementioned acidic group and the like, it may have two or more of the aforementioned acidic group and the like. In the case of having two or more of the above-mentioned acidic groups, etc., the above-mentioned acidic groups and the like having several may be the same or different. The number of the acidic groups and the like possessed by the compound of the general formula (2) is preferably 1 to 3, more preferably 1 to 2, and even more preferably one.

於上述通式(1)中Ra具有芳香族環、於上述通式(2)中Rb、Rb'及Rb"之至少一個具有芳香族環、以及於上述通式(3)中Rc及Rd之至少一個具有芳香族環之情況下,與下述色材之骨架之間 的親和性提高,色材分散性及分散穩定性變得優異,可獲得對比度優異之著色組成物,就上述方面而言較佳。 In the above general formula (1) wherein R a having an aromatic ring, in the general formula (2) R b, R b 'and R b "is at least one having an aromatic ring, and in the above general formula (3) When at least one of R c and R d has an aromatic ring, the affinity with the skeleton of the following color material is improved, the color material dispersibility and dispersion stability become excellent, and a coloring composition with excellent contrast can be obtained , It is better in terms of the above.

就提高色材分散性之方面而言,選自上述通式(1)~(3)所構成之群中之1種以上之化合物之分子量較佳為1000以下,其中較佳為50~800,進而較佳為50~400,進而更佳為80~350,最佳為100~330。 In terms of improving the dispersibility of color materials, the molecular weight of one or more compounds selected from the group consisting of the above general formulas (1) to (3) is preferably 1000 or less, and among them, 50 to 800 are preferred. More preferably, it is 50-400, still more preferably 80-350, and most preferably 100-330.

作為上述通式(1)所表示之化合物,例如可列舉:苯磺酸、乙烯基磺酸、甲磺酸、對甲苯磺酸、單甲基硫酸、單乙基硫酸、單正丙基硫酸等。再者,亦可使用如對甲苯磺酸水合物般之水合物。作為上述通式(2)所表示之化合物,例如可列舉:氯化甲基、溴化甲基、氯化乙基、溴化乙基、碘化甲基、碘化乙基、氯化正丁基、氯化己基、氯化辛基、氯化十二烷基、氯化十四烷基、氯化十六烷基、氯化苯乙基、氯化苄基、溴化苄基、碘化苄基、氯苯、α-氯苯基乙酸、α-溴苯基乙酸、α-碘苯基乙酸、4-氯甲基苯甲酸、4-溴甲基苯甲酸、4-碘苯基苯甲酸、氯乙酸、溴乙酸、碘乙酸、α-溴苯基乙酸甲酯、3-(溴甲基)苯基硼酸等。作為上述通式(3)所表示之化合物,例如可列舉:單丁基磷酸、二丁基磷酸、甲基磷酸、二苄基磷酸、二苯基磷酸、苯基次膦酸、苯基膦酸、二甲基丙烯醯氧基乙基酸式磷酸酯等。就分散穩定性尤其優異之方面而言,較佳為選自由苯基次膦酸、苯基膦酸、二甲基丙烯醯氧基乙基酸式磷酸酯、二丁基磷酸、氯化苄基、溴化苄基、乙烯基磺酸、及對甲苯磺酸-水合物所構成之群中之1種以上,其中較佳為使用選自由苯基次膦酸、苯基膦酸、氯化苄基、溴化苄基、及對甲苯磺酸-水合物所構成之群中之1種以上。又,就藉由與上述特定之嵌段共聚合體之組合而 提高顯影殘渣之抑制效果之方面而言,亦較佳地使用具有酸性基及其酯基之通式(2)所表示之化合物,其中亦較佳地使用選自由α-氯苯基乙酸、α-溴苯基乙酸、α-碘苯基乙酸、4-氯甲基苯甲酸、4-溴甲基苯甲酸及4-碘苯基苯甲酸所構成之群中之1種以上。 Examples of the compound represented by the general formula (1) include: benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, mono-n-propylsulfuric acid, etc. . Furthermore, hydrates such as p-toluenesulfonic acid hydrate can also be used. Examples of the compound represented by the general formula (2) include: methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, methyl iodide, ethyl iodide, and n-butyl chloride. Base, hexyl chloride, octyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, phenethyl chloride, benzyl chloride, benzyl bromide, iodide Benzyl, chlorobenzene, α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-iodophenylbenzoic acid , Chloroacetic acid, bromoacetic acid, iodoacetic acid, methyl α-bromophenylacetate, 3-(bromomethyl)phenylboronic acid, etc. Examples of the compound represented by the general formula (3) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenyl phosphinic acid, and phenyl phosphonic acid. , Dimethyl acryloxy ethyl acid phosphate, etc. In terms of particularly excellent dispersion stability, it is preferably selected from the group consisting of phenylphosphinic acid, phenylphosphonic acid, dimethylacryloxy ethyl acid phosphate, dibutyl phosphoric acid, and benzyl chloride. , Benzyl bromide, vinyl sulfonic acid, and p-toluenesulfonic acid-hydrate. Among them, it is preferable to use one selected from phenylphosphinic acid, phenylphosphonic acid, and benzyl chloride. One or more of the group consisting of benzyl bromide, benzyl bromide, and p-toluenesulfonic acid monohydrate. In addition, in terms of improving the effect of suppressing development residue by the combination with the above-mentioned specific block copolymer, it is also preferable to use a compound represented by the general formula (2) having an acidic group and its ester group, Among them, it is also preferably used selected from α-chlorophenylacetic acid, α-bromophenylacetic acid, α-iodophenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid and 4-iodophenyl One or more of the group consisting of benzoic acid.

於鹽型嵌段共聚合體中,關於選自由有機酸化合物及鹵代烴所構成之群中之至少一種之含量,由於與通式(I)所表示之構成單元所具有之末端之氮部位形成鹽,故而相對於通式(I)所表示之構成單元所具有之末端之氮部位,較佳為將選自由有機酸化合物及鹵代烴所構成之群中之至少一種之合計設為0.01莫耳以上,更佳為設為0.1莫耳以上,進而較佳為設為0.2莫耳以上,尤佳為設為0.3莫耳以上。若為上述下限值以上,則容易獲得由鹽形成所產生之提高色材分散性之效果。同樣地,較佳為設為1莫耳以下,更佳為設為0.8莫耳以下,進而較佳為設為0.7莫耳以下,尤佳為設為0.6莫耳以下。若為上述上限值以下,則可成為顯影密接性或溶劑再溶解性優異者。再者,選自由有機酸化合物及鹵代烴所構成之群中之至少一種可單獨使用1種,亦可組合2種以上。於組合2種以上之情況下,較佳為其合計含量為上述範圍內。 In the salt-type block copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is due to the fact that it is formed with the terminal nitrogen site of the structural unit represented by the general formula (I) Salt, therefore, it is preferable that the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0.01 moiety with respect to the terminal nitrogen site of the structural unit represented by the general formula (I). Ear or more, more preferably 0.1 mol or more, still more preferably 0.2 mol or more, and particularly preferably 0.3 mol or more. If it is more than the above lower limit, the effect of improving the dispersibility of the color material due to the salt formation is easily obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. If it is equal to or less than the above upper limit, it will be excellent in development adhesiveness or solvent resolubility. In addition, at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When combining two or more types, it is preferable that the total content is in the said range.

作為鹽型嵌段共聚合體之製備方法,可列舉於溶解或分散有鹽形成前之嵌段共聚合體之溶劑中,添加選自由上述有機酸化合物及鹵代烴所構成之群中之至少一種,並進行攪拌,進而視需要進行加熱之方法等。再者,嵌段共聚合體之該通式(I)所表示之構成單元所具有之末端之氮部位與選自由上述有機酸化合物及鹵代烴所構成之群中之至少一種形成鹽、及其比率可藉由例如核磁共振(NMR,Nuclear Magnetic Resonance)等公知之方法進行確認。 As a method for preparing the salt-type block copolymer, it can be exemplified by adding at least one selected from the group consisting of the above-mentioned organic acid compounds and halogenated hydrocarbons in a solvent in which the block copolymer before salt formation is dissolved or dispersed. And stirring, and then heating method as necessary. Furthermore, the terminal nitrogen portion of the structural unit represented by the general formula (I) of the block copolymer forms a salt with at least one selected from the group consisting of the above-mentioned organic acid compound and halogenated hydrocarbon, and The ratio can be confirmed by a known method such as Nuclear Magnetic Resonance (NMR).

所獲得之鹽型嵌段共聚合體之胺值與鹽形成前之嵌段共聚合體相比,值變小相應於形成鹽之量。但是,由於鹽形成部位與相當於胺基之末端之氮部位同樣、或者說為了成為經強化之色材吸附部位,故而有藉由鹽形成而使色材分散性或色材分散穩定性提高之傾向。又,鹽形成部位與胺基同樣地,若過多則對溶劑再溶解性造成不良影響。因此,於本發明中,可將鹽形成前之嵌段共聚合體之胺值作為用於使色材分散穩定性及溶劑再溶解性變得良好之指標。作為所獲得之鹽型嵌段共聚合體之胺值,較佳為0~130mgKOH/g,進而較佳為0~120mgKOH/g。若為上述上限值以下,則與其他成分之相溶性優異,溶劑再溶解性變得良好。 Compared with the block copolymer before salt formation, the amine value of the obtained salt-type block copolymer becomes smaller corresponding to the amount of salt formed. However, since the salt formation site is the same as the nitrogen site corresponding to the end of the amine group, or in order to become a strengthened color material adsorption site, the salt formation improves the color material dispersibility or the color material dispersion stability. tendency. In addition, the salt formation site is the same as the amine group, if too much, it will adversely affect the solvent resolubility. Therefore, in the present invention, the amine value of the block copolymer before salt formation can be used as an index for improving the dispersion stability of the color material and the solvent resolubility. The amine value of the obtained salt-type block copolymer is preferably 0 to 130 mgKOH/g, and more preferably 0 to 120 mgKOH/g. If it is less than the above upper limit, the compatibility with other components is excellent, and the solvent re-solubility becomes good.

再者,鹽型嵌段共聚合體中,藉由上述通式(2)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之胺值可設為藉由JIS K 7237:1995所記載之方法測得之值。其原因在於,上述通式(2)之化合物係通式(I)所表示之構成單元所具有之末端之氮部位與鹵素原子側烴形成鹽,因此即便藉由該測定方法,亦不會對鹽形成之狀態帶來變化,能夠測定胺值。另一方面,鹽型嵌段共聚合體中藉由上述通式(1)或(3)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之胺值可藉由根據上述鹽形成前之嵌段共聚合體之胺值,如下所述般算出而求出。其原因在於,上述通式(1)或(3)所表示之化合物係通式(I)所表示之構成單元所具有之末端之氮部位與酸性基形成鹽,因此若藉由上述JIS K 7237:1995所記載之方法測定此種鹽型嵌段共聚合體之胺值,則對鹽形成之狀態帶來變化,無法測定準確之值。首先,藉由上述方法,求出鹽形成前之嵌段共聚合體之胺值。其次,使用核磁共振裝置測定鹽型嵌段共聚合體之13C-NMR光 譜,於所獲得之光譜資料中,根據上述通式(I)所表示之構成單元所具有之末端之氮部位中未進行鹽形成之氮原子所鄰接之碳原子峰與進行鹽形成之氮原子所鄰接之碳原子峰之積分值之比率,測定鹽型嵌段共聚合體之選自由上述通式(1)或(3)所構成之群中之1種以上之化合物對於通式(I)所表示之構成單元所具有之末端之氮部位的反應率(進行鹽形成之末端之氮部位比率)。關於選自由上述通式(1)或(3)所構成之群中之1種以上之化合物進行鹽形成的通式(I)所表示之構成單元所具有之末端之氮部位,係將胺值設為0,自鹽形成前之嵌段共聚合體之胺值減去藉由(利用JIS K 7237:1995所記載之方法測得之鹽形成前嵌段共聚合體之胺值)×(由13C-NMR光譜算出之進行鹽形成之末端之氮部位比率(%)/100)而算出之因鹽形成所消耗之胺值,藉此求出該值。鹽型嵌段共聚合體之胺值={利用JIS K 7237:1995所記載之方法測得之鹽形成前嵌段共聚合體之胺值}-{利用JIS K 7237:1995所記載之方法測得之鹽形成前嵌段共聚合體之胺值}×{由13C-NMR光譜算出之鹽形成之末端之氮部位比率(%)/100} Furthermore, in the salt-type block copolymer, the amine value of the salt-type block copolymer formed by salt formation from the compound represented by the above general formula (2) can be set by the method described in JIS K 7237:1995 The measured value. The reason is that the compound of the above general formula (2) forms a salt with the halogen atom-side hydrocarbon at the terminal nitrogen portion of the structural unit represented by the general formula (I), and therefore, even by this measurement method, it will not affect The state of salt formation brings about changes, and the amine value can be measured. On the other hand, in the salt-type block copolymer, the amine value of the salt-type block copolymer formed by the compound represented by the above-mentioned general formula (1) or (3) can be determined by the amine value of the salt-type block copolymer before the formation of the salt. The amine value of the stage copolymer is calculated and determined as described below. The reason is that the compound represented by the above-mentioned general formula (1) or (3) forms a salt with an acidic group at the end of the structural unit represented by the general formula (I). Therefore, if the compound represented by the above-mentioned JIS K 7237 : The method described in 1995 to measure the amine value of this salt-type block copolymer will change the state of salt formation, and the accurate value cannot be measured. First, by the above method, the amine value of the block copolymer before salt formation is obtained. Next, the 13C-NMR spectrum of the salt-type block copolymer was measured using a nuclear magnetic resonance device. In the obtained spectrum data, the nitrogen portion of the terminal of the structural unit represented by the above general formula (I) was not salted. The ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom formed and the peak of the carbon atom adjacent to the nitrogen atom undergoing salt formation is determined. The salt type block copolymer is selected from the above general formula (1) or (3). The reaction rate of one or more compounds in the group to the terminal nitrogen site of the structural unit represented by the general formula (I) (the rate of the terminal nitrogen site that undergoes salt formation). Regarding the salt formation of one or more compounds selected from the group consisting of the above-mentioned general formula (1) or (3), the nitrogen site at the end of the structural unit represented by the general formula (I) is based on the amine value Set to 0, subtract from the amine value of the block copolymer before salt formation by (the amine value of the block copolymer before salt formation measured by the method described in JIS K 7237: 1995) × (from 13C- The value of the amine consumed due to salt formation calculated by the ratio of nitrogen sites at the end of salt formation (%)/100) calculated by NMR spectroscopy is used to obtain this value. The amine value of the salt-type block copolymer={Amine value of the block copolymer before salt formation measured by the method described in JIS K 7237:1995}-{Measured by the method described in JIS K 7237:1995 The amine value of the block copolymer before the salt formation}×{The ratio of the nitrogen site at the end of the salt formation calculated from the 13C-NMR spectrum (%)/100}

本發明所使用之分散劑之酸值並無特別限定,其中就顯影密接性及溶劑再溶解性變得良好之方面而言,較佳為18mgKOH/g以下,更佳為12mgKOH/g以下。另一方面,就進一步提高溶劑再溶解性及顯影密接性之方面、基板密接性及分散穩定性之方面而言,本發明所使用之分散劑之酸值較佳為0mgKOH/g。酸值越小,則越不易受到鹼性顯影液之侵蝕,因此視為顯影密接性變得良好者。另一方面,就顯影殘渣之抑制效果之方面而言,較佳為1mgKOH/g以上,更佳為2mgKOH/g以上。於本發明所使用之分 散劑中,就顯影密接性及溶劑再溶解性變得良好之方面而言,鹽形成前之嵌段共聚合體之酸值較佳為18mgKOH/g以下,更佳為12mgKOH/g以下。又,就進一步提高溶劑再溶解性與顯影密接性之方面,及基板密接性與分散穩定性之方面而言,鹽形成前之嵌段共聚合體之酸值較佳為0mgKOH/g。另一方面,就顯影殘渣之抑制效果之方面而言,較佳為1mgKOH/g以上,更佳為2mgKOH/g以上。 The acid value of the dispersant used in the present invention is not particularly limited, but it is preferably 18 mgKOH/g or less, more preferably 12 mgKOH/g or less in terms of developing adhesion and solvent resolubility. On the other hand, the acid value of the dispersant used in the present invention is preferably 0 mgKOH/g in terms of further improving solvent resolubility and development adhesiveness, substrate adhesiveness and dispersion stability. The smaller the acid value, the less likely it is to be corroded by the alkaline developer, so it is considered that the development adhesiveness becomes better. On the other hand, in terms of the effect of suppressing development residues, it is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more. In the dispersant used in the present invention, the acid value of the block copolymer before salt formation is preferably 18 mgKOH/g or less, more preferably 12 mgKOH in terms of developing adhesion and solvent re-solubility. /g or less. In addition, in terms of further improving solvent resolubility and development adhesion, and in terms of substrate adhesion and dispersion stability, the acid value of the block copolymer before salt formation is preferably 0 mgKOH/g. On the other hand, in terms of the effect of suppressing development residues, it is preferably 1 mgKOH/g or more, and more preferably 2 mgKOH/g or more.

如上所述,鹽形成前之嵌段共聚合體之酸值表示用以中和嵌段共聚合體之固形物成分1g中所含之酸性成分所需要之氫氧化鉀之質量(mg),係藉由JIS K 0070:1992所記載之方法而測得之值。又,關於鹽型嵌段共聚合體,藉由上述通式(2)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之酸值亦為藉由JIS K 0070:1992所記載之方法而測得之值。其原因在於,上述通式(2)之化合物係通式(I)所表示之構成單元所具有之末端之氮部位與鹵素原子側烴形成鹽,因此即便藉由該測定方法,亦不會對鹽形成之狀態帶來變化,能夠進行測定。另一方面,於鹽型嵌段共聚合體為藉由上述通式(1)或(3)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之情況下,去除用於鹽形成之酸性基而算出酸值。其原因在於,用於鹽形成之酸性基無法發揮作為使分散劑之酸值增加之酸性基之功能。因此,本案中,藉由上述通式(1)或(3)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之酸值係以藉由下述式所獲得之值算出。其原因在於,若利用上述JIS K 0070:1992所記載之方法測定藉由上述通式(1)或(3)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之酸值,則對鹽形成之狀態帶來變化,無法測定準確之值。 As mentioned above, the acid value of the block copolymer before salt formation means the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1g of the solid component of the block copolymer, by Measured by the method described in JIS K 0070: 1992. In addition, regarding the salt-type block copolymer, the acid value of the salt-type block copolymer formed by salt formation from the compound represented by the above general formula (2) is also measured by the method described in JIS K 0070: 1992 Got the value. The reason is that the compound of the above general formula (2) forms a salt with the halogen atom-side hydrocarbon at the terminal nitrogen portion of the structural unit represented by the general formula (I), and therefore, even by this measurement method, it will not affect The state of salt formation brings about changes and can be measured. On the other hand, when the salt-type block copolymer is a salt-type block copolymer in which salt is formed by the compound represented by the above general formula (1) or (3), the acidic group used for salt formation is removed And calculate the acid value. The reason is that the acidic group used for salt formation cannot function as an acidic group that increases the acid value of the dispersant. Therefore, in this case, the acid value of the salt-type block copolymer formed by salt formation with the compound represented by the above general formula (1) or (3) is calculated from the value obtained by the following formula. The reason is that if the acid value of the salt type block copolymer formed by the compound represented by the general formula (1) or (3) is measured by the method described in JIS K 0070: 1992, the salt The state of formation brings about changes, and the exact value cannot be measured.

鹽型嵌段共聚合體之酸值={用於鹽形成之上述通式 (1)或(3)所表示之化合物之總酸值-鹽形成所消耗之酸值)+鹽形成前嵌段共聚合體之酸值 The acid value of the salt-type block copolymer = (total acid value of the compound represented by the above general formula (1) or (3) used for salt formation-acid value consumed for salt formation) + block copolymerization before salt formation The acid value of the body

此處,上述用於鹽形成之上述通式(1)或(3)所表示之化合物之總酸值可藉由上述JIS K 0070:1992所記載之方法進行測定。另一方面,關於鹽形成所消耗之酸值,由藉由NMR所獲得之鹽形成比率算出。具體而言,鹽形成所消耗之酸值例如使用核磁共振裝置測定鹽型嵌段共聚合體之13C-NMR光譜,於所獲得之光譜資料中,根據在末端之氮部位中未進行鹽形成之氮原子所鄰接之碳原子峰與進行鹽形成之氮原子所鄰接之碳原子峰之積分值之比率,算出進行鹽形成之末端之氮部位數相對於末端之氮部位總數之比率。藉由{利用JIS K 7237:1995所記載之方法測得之鹽形成前嵌段共聚合體之胺值}×{由13C-NMR光譜算出之進行鹽形成之末端之氮部位比率(%)/100},算出消耗之胺值,該值與鹽形成所消耗之酸值成為相同之值。但是,於相對於通式(I)所表示之構成單元所具有之末端之氮部位,以上述通式(1)所表示之化合物為1莫耳以下進行鹽形成之情況下,以具有1個酸性基之上述通式(3)所表示之化合物為1莫耳以下進行鹽形成之情況下,或以具有2個酸性基之上述通式(3)所表示之化合物為0.5莫耳以下進行鹽形成之情況下,關於酸性基之總量,只要與通式(I)所表示之構成單元所具有之末端之氮部位形成鹽,則於鹽形成後之鹽型嵌段共聚合體中,該酸性基不會對酸值造成影響,因此可具有與鹽形成前之嵌段共聚合體相同之酸值。另一方面,於以超出上述之莫耳數添加具有2個酸性基之上述通式(3)所表示之化合物之情況下,於鹽形成後亦於分散劑中存在未進行鹽形成之酸性基,因此如上述式所示,將未進行鹽形成之酸性基之量 的酸值與鹽形成前之嵌段共聚合體之酸值相加,算出分散劑之酸值。 Here, the total acid value of the compound represented by the above general formula (1) or (3) used for salt formation can be measured by the method described in the above JIS K 0070:1992. On the other hand, the acid value consumed for salt formation was calculated from the salt formation ratio obtained by NMR. Specifically, the acid value consumed for salt formation, for example, is measured by the 13C-NMR spectrum of the salt-type block copolymer using a nuclear magnetic resonance device, and the obtained spectrum data is based on the nitrogen in the terminal nitrogen site that has not undergone salt formation. The ratio of the integral value of the carbon atom peak adjacent to the atom to the carbon atom peak adjacent to the nitrogen atom undergoing salt formation is calculated as the ratio of the number of nitrogen sites at the end of the salt formation to the total number of nitrogen sites at the end. By {the amine value of the block copolymer before the salt formation measured by the method described in JIS K 7237:1995}×{calculated from 13C-NMR spectrum the ratio of the nitrogen site at the end of the salt formation (%)/100 }, calculate the consumed amine value, which is the same value as the acid value consumed for salt formation. However, when the compound represented by the general formula (1) is 1 mol or less to form a salt with respect to the nitrogen site at the terminal of the structural unit represented by the general formula (I), it may have one When the compound represented by the above general formula (3) of the acidic group is 1 mol or less for salt formation, or the compound represented by the above general formula (3) having 2 acidic groups is 0.5 mol or less for the salt formation In the case of formation, as long as the total amount of acidic groups forms a salt with the terminal nitrogen site of the structural unit represented by the general formula (I), the acidic block copolymer in the salt-type block copolymer after salt formation The base does not affect the acid value, so it can have the same acid value as the block copolymer before the salt is formed. On the other hand, when the compound represented by the above-mentioned general formula (3) having two acidic groups is added in a molar number exceeding the above-mentioned number of moles, there are acidic groups that have not undergone salt formation in the dispersant after the salt is formed. Therefore, as shown in the above formula, the acid value of the amount of acidic groups that have not undergone salt formation is added to the acid value of the block copolymer before salt formation to calculate the acid value of the dispersant.

又,於本發明中,分散劑之羥值較佳為120mgKOH/g以下,更佳為80mgKOH/g以下,進而更佳為60mgKOH/g以下。若分散劑之羥值過高,則有溶劑再溶解性降低之情況。另一方面,就分散性及分散穩定性之方面而言,分散劑之羥值較佳為2mgKOH/g以上,更佳為5mgKOH/g以上。再者,本發明中,羥值表示中和與由固形物成分1g所獲得之乙醯化物結合之乙酸所需要之KOH之質量(mg),係指依據JIS K 0070:1992,藉由電位差滴定法而求出之值。 Furthermore, in the present invention, the hydroxyl value of the dispersant is preferably 120 mgKOH/g or less, more preferably 80 mgKOH/g or less, and still more preferably 60 mgKOH/g or less. If the hydroxyl value of the dispersant is too high, the re-solubility of the solvent may decrease. On the other hand, in terms of dispersibility and dispersion stability, the hydroxyl value of the dispersant is preferably 2 mgKOH/g or more, more preferably 5 mgKOH/g or more. Furthermore, in the present invention, the hydroxyl value refers to the mass (mg) of KOH required to neutralize the acetic acid bound to the acetyl compound obtained from 1g of the solid content, and refers to titration by potentiometric titration in accordance with JIS K 0070: 1992 The value obtained by the law.

於本發明之色材分散液中,作為分散劑,使用上述嵌段共聚合體及鹽型嵌段共聚合體之至少一種,其含量根據所使用之色材之種類、進而根據下述彩色濾光片用感光性著色樹脂組成物中之固形物成分濃度等而適當選定。分散劑之含量相對於色材分散液中之總固形物成分100質量份,較佳為以3~45質量份,更佳為以5~35質量份之比率調配。若為上述下限值以上,則色材之分散性及分散穩定性優異,彩色濾光片用感光性著色樹脂組成物之保存穩定性更優異。又,若為上述上限值以下,則顯影性變得良好。尤其於形成色材濃度較高之塗膜或著色層之情況下,分散劑之含量相對於色材分散液中之總固形物成分100質量份,較佳為以3~25質量份、更佳為以5~20質量份之比率調配。再者,本發明中,固形物成分係指上述溶劑以外之所有者,亦包括溶解於溶劑中之單體等。 In the color material dispersion of the present invention, as a dispersant, at least one of the above-mentioned block copolymer and salt type block copolymer is used, and the content depends on the type of color material used, and further according to the following color filter The concentration of the solid content in the photosensitive colored resin composition is appropriately selected. The content of the dispersant relative to 100 parts by mass of the total solid content in the color material dispersion is preferably 3 to 45 parts by mass, more preferably 5 to 35 parts by mass. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of the photosensitive colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a coating film or colored layer with a high color material concentration, the content of the dispersant is preferably 3-25 parts by mass, more preferably 3-25 parts by mass, relative to 100 parts by mass of the total solid content in the color material dispersion. It is formulated at a ratio of 5-20 parts by mass. Furthermore, in the present invention, the solid content refers to owners other than the above-mentioned solvent, and also includes monomers dissolved in the solvent, etc.

<色材> <color material>

本發明中,色材只要為於形成彩色濾光片之著色層時能夠實現所期望之顯色者即可,並無特別限定,可將各種有機顏料、無機顏料、能夠分散之染料、染料之成鹽化合物等單獨使用或混合2種以上而使用。其中,有機顏料由於顯色性較高且耐熱性亦較高,故而較佳地使用。作為有機顏料,例如可列舉於色指數(C.I.;The Society of Dyers and Colourists公司發行)中分類為顏料(Pigment)之化合物,具體而言可列舉如下所述之附有色指數(C.I.)編號者。 In the present invention, the color material is not particularly limited as long as it can achieve the desired color development when forming the coloring layer of the color filter. Various organic pigments, inorganic pigments, dispersible dyes, and dyes can be used. A salt-forming compound etc. are used individually or in mixture of 2 or more types. Among them, organic pigments are preferably used due to higher color rendering properties and higher heat resistance. Examples of organic pigments include compounds classified as pigments in the color index (C.I.; issued by The Society of Dyers and Colourists), and specifically, those with a color index (C.I.) number as described below can be cited.

C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、55、60、61、65、71、73、74、81、83、93、95、97、98、100、101、104、106、108、109、110、113、114、116、117、119、120、126、127、128、129、138、139、150、151、152、153、154、155、156、166、168、175、185、及C.I.顏料黃150之衍生物顏料;C.I.顏料橙1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73;C.I.顏料紫1、19、23、29、32、36、38;C.I.顏料紅1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、193、194、202、206、207、208、209、215、216、220、224、226、242、243、245、254、255、264、265、272;C.I.顏料藍15、15:3、15:4、15:6、60;C.I.顏料綠7、36、58、59;C.I.顏料 棕23、25;C.I.顏料黑1、7。 CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98 , 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155 , 156, 166, 168, 175, 185, and CI Pigment Yellow 150 derivative pigments; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 272; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; CI Pigment Green 7, 36, 58, 59; CI Pigment Brown 23, 25; CI Pigment Black 1, 7.

又,作為上述無機顏料之具體例,可列舉:氧化鈦、硫酸鋇、碳酸鈣、鋅白、硫酸鉛、黃丹、鋅黃、鐵丹(氧化鐵紅(III))、鎘紅、群青、鐵藍、氧化鉻綠、鈷綠、棕土、鈦黑、合成鐵黑、碳黑等。 In addition, specific examples of the above-mentioned inorganic pigments include: titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow plum, zinc yellow, iron plum (iron oxide red (III)), cadmium red, ultramarine, Iron blue, chrome oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

例如於在彩色濾光片之基板上以本發明之色材分散液為下述彩色濾光片用感光性著色樹脂組成物而形成遮光層之圖案之情況下,於墨水中調配遮光性較高之黑色顏料。作為遮光性較高之黑色顏料,例如可使用碳黑或四氧化三鐵等無機顏料、或花青黑等有機顏料。 For example, when the color material dispersion of the present invention is used as the following photosensitive colored resin composition for color filters to form the pattern of the light-shielding layer on the substrate of the color filter, the light-shielding property is higher when blended in the ink The black pigment. As black pigments with high light-shielding properties, for example, inorganic pigments such as carbon black or triiron tetroxide, or organic pigments such as cyanine black can be used.

作為上述能夠分散之染料,可列舉藉由對染料賦予各種取代基或與溶解度較低之溶劑組合使用而能夠分散之染料。作為染料之成鹽化合物,係指染料與相對離子形成鹽之化合物,例如可列舉鹼性染料與酸之成鹽化合物、酸性染料與鹼之成鹽化合物,亦包括使用公知之色澱化(成鹽化)方法將可溶性染料溶解於溶劑中,於溶劑中不溶化之色澱顏料。本發明中,藉由將包含選自染料及染料之成鹽化合物中之至少一種之色材與上述本發明之分散劑組合而使用,可提高該色材之分散性或分散穩定性。 Examples of the above-mentioned dispersible dyes include dyes that can be dispersible by imparting various substituents to the dye or using it in combination with a solvent with low solubility. The salt-forming compound of the dye refers to a compound in which the dye forms a salt with an opposite ion. For example, a salt-forming compound of a basic dye and an acid, and a salt-forming compound of an acid dye and a base are included. The salting method is to dissolve the soluble dye in the solvent, and the lake pigment that is insoluble in the solvent. In the present invention, the dispersibility or dispersion stability of the color material can be improved by using a color material containing at least one selected from a dye and a salt-forming compound of the dye in combination with the above-mentioned dispersant of the present invention.

作為上述染料,可自習知公知之染料中適當選擇。作為此種染料,例如可列舉:偶氮染料、金屬錯鹽偶氮染料、蒽醌染料、三苯基甲烷染料、

Figure 107106607-A0101-12-0044-36
染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。再者,作為標準,只要相對於10g之溶劑(或混合溶劑),染料之溶解量為10mg以下,則判定為該染料能夠於該溶劑(或混合溶劑)中分散。 As the above-mentioned dye, it can be suitably selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes,
Figure 107106607-A0101-12-0044-36
Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc. Furthermore, as a standard, as long as the dissolved amount of the dye is 10 mg or less with respect to 10 g of the solvent (or mixed solvent), it is determined that the dye can be dispersed in the solvent (or mixed solvent).

其中,於色材含有選自由吡咯并吡咯二酮顏料、喹酞酮顏料、酞菁銅顏料、酞菁鋅顏料、喹酞酮染料、香豆素染料、花青染料及該等染料之成鹽化合物所構成之群中之至少一種之情況下,就抑制因使用上述分散劑所引起之色材之昇華或析出之效果較高,可形成高亮度之著色層之方面而言較佳。又,作為上述色材,其中較佳為含有選自由吡咯并吡咯二酮顏料、喹酞酮顏料、酞菁銅顏料、酞菁鋅顏料、喹酞酮染料所構成之群中之至少一種。 Among them, the color material contains diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salts of these dyes. In the case of at least one of the group consisting of the compound, the effect of suppressing the sublimation or precipitation of the color material caused by the use of the above-mentioned dispersing agent is high, and a high-brightness colored layer can be formed. In addition, as the color material, it is preferable to contain at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.

作為吡咯并吡咯二酮顏料,例如可列舉C.I.顏料紅254、255、264、272、及下述通式(i)所表示之吡咯并吡咯二酮顏料,其中較佳為選自C.I.顏料紅254、272、及於下述通式(i)中R21及R22分別為4-溴苯基之吡咯并吡咯二酮顏料中之至少一種。 As the diketopyrrolopyrrole pigment, for example, CI Pigment Red 254, 255, 264, 272, and the diketopyrrolopyrrole pigment represented by the following general formula (i) can be cited. Among them, it is preferably selected from CI Pigment Red 254 , 272, and in the following general formula (i), R 21 and R 22 are each at least one of 4-bromophenyl diketopyrrolopyrrole pigments.

Figure 107106607-A0101-12-0045-13
Figure 107106607-A0101-12-0045-13

(通式(i)中,R21及R22分別獨立為4-氯苯基或4-溴苯基) (In the general formula (i), R 21 and R 22 are each independently 4-chlorophenyl or 4-bromophenyl)

作為喹酞酮顏料,例如可列舉C.I.顏料黃138等。作為酞菁銅顏料,例如可列舉:C.I.顏料藍15、15:1、15:2、15:3、15:4、15:5、15:6、C.I.顏料綠7、36等,其中較佳為C.I.顏料藍15:6。作為酞菁鋅顏料,例如可列舉:C.I.顏料綠58、59等。作為喹酞酮染料,例如可列舉:C.I.分散黃54、64、67、134、149、 160、C.I.溶劑黃114、157等,其中較佳為C.I.分散黃54。 As a quinophthalone pigment, C.I. Pigment Yellow 138 etc. are mentioned, for example. Examples of copper phthalocyanine pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, CI Pigment Green 7, 36, etc. It is CI Pigment Blue 15:6. As a zinc phthalocyanine pigment, C.I. Pigment Green 58, 59 etc. are mentioned, for example. Examples of the quinophthalone dye include: C.I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. Solvent Yellow 114, 157, etc. Among them, C.I. Disperse Yellow 54 is preferred.

作為本發明所使用之色材之平均一次粒徑,於設為彩色濾光片之著色層之情況下,只要為能實現所期望之顯色者即可,並無特別限定,亦根據所使用之色材之種類而不同,較佳為10~100nm之範圍內,更佳為15~60nm。藉由使色材之平均一次粒徑為上述範圍,可使具備使用本發明之色材分散液製造之彩色濾光片之顯示裝置成為高對比度且高品質者。 As the average primary particle size of the color material used in the present invention, when it is used as the coloring layer of a color filter, it is not particularly limited as long as it can achieve the desired color development. The type of color material varies, preferably in the range of 10-100nm, more preferably 15-60nm. By setting the average primary particle size of the color material within the above range, a display device equipped with a color filter manufactured using the color material dispersion liquid of the present invention can be a high-contrast and high-quality display device.

又,色材分散液中之色材之平均分散粒徑亦根據所使用之色材之種類而不同,較佳為10~100nm之範圍內,更佳為15~60nm之範圍內。色材分散液中之色材之平均分散粒徑係分散於至少含有溶劑之分散介質中之色材粒子之分散粒徑,且係藉由雷射光散射粒度分佈計而測定。作為利用雷射光散射粒度分佈計進行之粒徑之測定,可藉由色材分散液所使用之溶劑將色材分散液適當稀釋(例如1000倍等)至能夠以雷射光散射粒度分佈計測定之濃度,使用雷射光散射粒度分佈計(例如日機裝公司製造之Nanotrac粒度分佈測定裝置UPA-EX150)藉由動態光散射法於23℃下進行測定。此處之平均分佈粒徑為體積平均粒徑。 In addition, the average dispersed particle diameter of the color material in the color material dispersion liquid also differs according to the type of color material used, and is preferably in the range of 10 to 100 nm, and more preferably in the range of 15 to 60 nm. The average dispersed particle diameter of the color material in the color material dispersion is the dispersed particle diameter of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. For the measurement of particle size using a laser light scattering particle size distribution meter, the color material dispersion liquid can be appropriately diluted (for example, 1000 times, etc.) with the solvent used in the color material dispersion liquid to a concentration that can be measured by the laser light scattering particle size distribution meter , Use a laser light scattering particle size distribution meter (for example, Nanotrac particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.) to measure by dynamic light scattering at 23°C. The average distribution particle size here is the volume average particle size.

本發明所使用之色材可藉由再結晶法、溶劑鹽磨法等公知方法進行製造。又,亦可將市售之色材進行微細化處理而使用。 The color material used in the present invention can be produced by a known method such as a recrystallization method and a solvent salt milling method. In addition, a commercially available color material can also be used by subjecting it to finer processing.

於本發明之色材分散液中,色材之含量並無特別限定。關於色材之含量,就分散性及分散穩定性之方面而言,相對於色材分散液中之總固形物成分100質量份,較佳為以5~80質量份、更佳為以8~70質量份之比率調配。尤其於形成色材濃度較高之塗膜或著色層之情況下,相對於色材分散液中之總固形物成分 100質量份,較佳為以30~80質量份、更佳為以40~75質量份之比率調配。 In the color material dispersion of the present invention, the content of the color material is not particularly limited. Regarding the content of the color material, in terms of dispersibility and dispersion stability, it is preferably 5 to 80 parts by mass, more preferably 8 to 100 parts by mass relative to 100 parts by mass of the total solid content in the color material dispersion. Blended at a ratio of 70 parts by mass. Especially in the case of forming a coating film or a colored layer with a high color material concentration, relative to 100 parts by mass of the total solid content in the color material dispersion, it is preferably 30 to 80 parts by mass, more preferably 40 to 40 parts by mass. Blended at a ratio of 75 parts by mass.

<溶劑> <Solvent>

作為本發明所使用之溶劑,只要為不與色材分散液中之各成分反應,且能夠將該等溶解或分散之有機溶劑即可,並無特別限定。溶劑可單獨使用或組合2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、環己醇乙酸酯等酯系溶劑;丙酮、甲基乙基酮、甲基異丁基酮、環己酮、2-庚酮等酮系溶劑;乙酸甲氧基乙酯、丙二醇單甲醚乙酸酯、3-甲氧基-3-甲基-1-乙酸丁酯、3-甲氧基乙酸丁酯、乙酸乙氧基乙酯等二醇醚乙酸酯系溶劑;乙酸甲氧基乙氧基乙酯、乙酸乙氧基乙氧基乙酯、丁基卡必醇乙酸酯(BCA)等卡必醇乙酸酯系溶劑;丙二醇二乙酸酯、1,3-丁二醇二乙酸酯等二乙酸酯類;乙二醇單甲醚、乙二醇單乙醚、乙二醇二甲醚、二乙二醇二甲醚、二乙二醇單乙醚、二乙二醇二乙醚、丙二醇單甲醚、二丙二醇二甲醚等二醇醚系溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等非質子性醯胺溶劑;γ-丁內酯等內酯系溶劑;四氫呋喃等環狀醚系溶劑;苯、甲苯、二甲苯、萘等不飽和烴系溶劑;N-庚烷、N-己烷、N-辛烷等飽和烴系溶劑;甲苯、二甲苯等芳香族烴類等有機溶劑。於該等溶劑中, 就其他成分之溶解性之方面而言,較佳為使用二醇醚乙酸酯系溶劑、卡必醇乙酸酯系溶劑、二醇醚系溶劑、酯系溶劑。其中,作為本發明所使用之溶劑,就其他成分之溶解性或塗佈適性之方面而言,較佳為選自由丙二醇單甲醚乙酸酯、丙二醇單甲醚、丁基卡必醇乙酸酯(BCA)、3-甲氧基-3-甲基-1-乙酸丁酯、乙氧基丙酸乙酯、乳酸乙酯、及3-甲氧基乙酸丁酯所構成之群中之1種以上。 The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material dispersion liquid and can dissolve or disperse the same. A solvent can be used individually or in combination of 2 or more types. Specific examples of solvents include, for example, alcoholic solvents such as methanol, ethanol, N-propanol, isopropanol, methoxy alcohol, and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxy Carbitol 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, cyclohexanol acetate and other ester solvents; acetone, methyl ethyl Ketone solvents such as ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.; methoxy ethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1- Glycol ether acetate solvents such as butyl acetate, 3-methoxy butyl acetate, and ethoxy ethyl acetate; methoxy ethoxy ethyl acetate, ethoxy ethoxy ethyl acetate, butyl Carbitol acetate solvents such as base carbitol acetate (BCA); diacetates such as propylene glycol diacetate and 1,3-butanediol diacetate; ethylene glycol monomethyl ether, Glycol ether series such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, and dipropylene glycol dimethyl ether Solvents; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone-based solvents such as γ-butyrolactone; Cyclic ether solvents such as tetrahydrofuran; unsaturated hydrocarbon solvents such as benzene, toluene, xylene, naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; aromatics such as toluene and xylene Organic solvents such as hydrocarbons. Among these solvents, in terms of solubility of other components, it is preferable to use glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents. Among them, the solvent used in the present invention is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and butyl carbitol acetic acid in terms of solubility or coating suitability of other components. Ester (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxy butyl acetate More than species.

本發明之色材分散液較佳為使如上溶劑相對於含有該溶劑之色材分散液總量通常為55~95質量%之範圍內,其中較佳為65~90質量%之範圍內,更佳為70~88質量%之範圍內。若溶劑過少,則黏度上升,分散性容易降低。又,若溶劑過多,則有色材濃度降低而難以達成目標之色度座標之情況。 The color material dispersion of the present invention is preferably such that the above solvent is usually in the range of 55 to 95% by mass relative to the total amount of the color material dispersion containing the solvent, and preferably in the range of 65 to 90% by mass, and more It is preferably in the range of 70 to 88% by mass. If the solvent is too small, the viscosity will increase and the dispersibility will tend to decrease. In addition, if the solvent is too much, the concentration of the colored material decreases and it is difficult to achieve the target chromaticity coordinates.

<其他成分> <Other ingredients>

於本發明之色材分散液中,只要無損本發明之效果,則亦可視需要進而調配分散輔助樹脂、其他成分。作為分散輔助樹脂,例如可列舉下述彩色濾光片用感光性著色樹脂組成物中例示之鹼可溶性樹脂。有如下情況:藉由鹼可溶性樹脂之立體阻礙而使色材粒子彼此不易接觸,藉由分散穩定化或其分散穩定化效果而有減少分散劑之效果。又,作為其他成分,例如可列舉用於提高潤濕性之界面活性劑、用於提高密接性之矽烷偶合劑、消泡劑、防收縮劑、抗氧化劑、防凝聚劑、紫外線吸收劑等。 In the color material dispersion of the present invention, as long as the effect of the present invention is not impaired, a dispersion auxiliary resin and other components may be further formulated as needed. Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified in the following photosensitive colored resin composition for color filters. There are cases where the color material particles are not easily contacted by the steric hindrance of the alkali-soluble resin, and the dispersion stabilization or its dispersion stabilization effect has the effect of reducing the dispersant. In addition, as other components, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, defoaming agents, anti-shrinking agents, antioxidants, anti-cohesion agents, ultraviolet absorbers, etc. can be cited.

本發明之色材分散液係用作用以製備下述彩色濾光片用感光性著色樹脂組成物之預製備物。即,所謂色材分散液係指於製備下述彩色濾光片用感光性著色樹脂組成物之前階段預先製 備之(組成物中之色材成分質量)/(組成物中之色材成分以外之固形物成分質量)比較高之色材分散液。具體而言,(組成物中之色材成分質量)/(組成物中之色材成分以外之固形物成分質量)比通常為1.0以上。藉由將色材分散液與下述各成分進行混合,可製備分散性優異之彩色濾光片用感光性著色樹脂組成物。 The color material dispersion of the present invention is used as a preliminary preparation for preparing the following photosensitive colored resin composition for color filters. In other words, the so-called color material dispersion refers to (the mass of the color material in the composition)/(the color material in the composition other than the color material in the composition) prepared in advance before the preparation of the photosensitive colored resin composition for the color filter below. The quality of solid content) is relatively high color material dispersion liquid. Specifically, the ratio of (mass of color material components in the composition)/(mass of solid components other than the color material components in the composition) is usually 1.0 or more. By mixing the color material dispersion liquid with the following components, a photosensitive colored resin composition for color filters with excellent dispersibility can be prepared.

<色材分散液之製造方法> <Method for manufacturing color material dispersion>

於本發明中,色材分散液之製造方法若為可獲得藉由上述嵌段其共聚合體或鹽型嵌段共聚合體之分散劑將上述色材分散於溶劑中而成之色材分散液的方法,則無特別限定。其中,就色材之分散性及分散穩定性優異之方面而言,較佳為設為以下之兩種製造方法中之任一者。 In the present invention, if the method for producing the color material dispersion liquid is such that a color material dispersion liquid obtained by dispersing the color material in a solvent by the dispersant of the block copolymer or salt type block copolymer can be obtained The method is not particularly limited. Among them, in terms of excellent dispersibility and dispersion stability of the color material, it is preferably set to either of the following two production methods.

即,本發明之色材分散液之第一製造方法具備如下步驟:準備上述嵌段共聚合體或鹽型嵌段共聚合體之分散劑;及於溶劑中,於上述分散劑之存在下使色材分散。 That is, the first production method of the color material dispersion of the present invention has the following steps: preparing a dispersant for the block copolymer or salt type block copolymer; and making the color material in the presence of the dispersant in a solvent dispersion.

又,使用作為鹽型嵌段共聚合體之分散劑之情況下之本發明之色材分散液之第二製造方法具有如下步驟:一面將溶劑、上述嵌段共聚合體、有機酸化合物等及色材進行混合,而使上述通式(I)所表示之構成單元所具有之末端之氮部位之至少一部分與有機酸化合物等形成鹽,一面使色材分散。 In addition, the second method of producing the color material dispersion of the present invention when used as a dispersant for the salt-type block copolymer has the following steps: at the same time, the solvent, the block copolymer, the organic acid compound, etc., and the color material By mixing, at least a part of the terminal nitrogen site of the structural unit represented by the general formula (I) forms a salt with an organic acid compound, etc., while dispersing the color material.

於使用鹽型嵌段共聚合體之情況下,根據上述第一製造方法,於製備鹽型嵌段共聚合體後,使用該鹽型嵌段共聚合體作為分散劑而使色材分散,因此可準確地確認鹽形成前之嵌段共聚合體與有機酸化合物等之反應終點或反應率,就該方面而言較佳。 又,根據上述第二製造方法,一面製備鹽型嵌段共聚合體之分散劑一面使色材分散,因此鹽型嵌段共聚合體不會自凝聚,可高效率地製備色材分散液,又,可提高分散性。 In the case of using a salt-type block copolymer, according to the first manufacturing method described above, after the salt-type block copolymer is prepared, the salt-type block copolymer is used as a dispersant to disperse the color material, so that the color material can be dispersed accurately. It is preferable in this respect to confirm the reaction end point or reaction rate of the block copolymer and the organic acid compound before salt formation. In addition, according to the second manufacturing method described above, the color material is dispersed while preparing the dispersant for the salt-type block copolymer. Therefore, the salt-type block copolymer does not self-agglomerate, and the color material dispersion can be prepared efficiently. Can improve dispersion.

於上述第一製造方法及上述第二製造方法中,色材可使用習知公知之分散機進行分散。作為分散機之具體例,可列舉:兩輥、三輥等輥磨機、球磨機、振動球磨機等球磨機、塗料調節器、連續盤形珠磨機、連續環形珠磨機等珠磨機。作為珠磨機之較佳之分散條件,使用之珠粒直徑較佳為0.03~3.0mm,更佳為0.05~2.0mm。 In the above-mentioned first manufacturing method and the above-mentioned second manufacturing method, the color material can be dispersed using a conventionally known dispersing machine. Specific examples of the dispersing machine include roller mills such as two-roll and three-roll mills, ball mills such as ball mills, vibrating ball mills, paint conditioners, continuous disc bead mills, continuous annular bead mills, and other bead mills. As a preferable dispersion condition of the bead mill, the diameter of the beads used is preferably 0.03~3.0mm, more preferably 0.05~2.0mm.

具體而言,可列舉:以珠粒直徑相對較大之2.0mm氧化鋯珠進行預分散,進而以珠粒直徑相對較小之0.1mm氧化鋯珠進行正式分散。又,分散後,較佳為以0.5~2μm之過濾器進行過濾。 Specifically, it can be exemplified by pre-dispersing with 2.0 mm zirconia beads with a relatively large bead diameter, and then performing formal dispersion with 0.1 mm zirconia beads with a relatively small bead diameter. Furthermore, after dispersion, it is preferable to filter with a filter of 0.5 to 2 μm.

II.彩色濾光片用感光性著色樹脂組成物 II. Photosensitive colored resin composition for color filters

本發明之彩色濾光片用感光性著色樹脂組成物之特徵在於含有上述本發明之色材分散液、鹼可溶性樹脂、多官能單體及光起始劑。本發明之彩色濾光片用感光性著色樹脂組成物藉由使用上述本發明之色材分散液,可形成高亮度之著色層,可抑制鄰接於著色層上而形成之ITO膜之龜裂。 The photosensitive colored resin composition for a color filter of the present invention is characterized by containing the color material dispersion liquid of the present invention, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator. The photosensitive colored resin composition for color filters of the present invention can form a high-brightness colored layer by using the color material dispersion liquid of the present invention, and can suppress cracks in the ITO film formed adjacent to the colored layer.

本發明之彩色濾光片用感光性著色樹脂組成物至少含有色材、分散劑、溶劑、鹼可溶性樹脂、多官能單體及光起始劑,亦可於無損本發明之效果之範圍內進而含有其他成分。以下,對本發明之彩色濾光片用感光性著色樹脂組成物中所含之各成分進行 說明,關於分散劑、色材、及溶劑,由於與上述本發明之色材分散液中所說明者相同,因此省略此處之說明。 The photosensitive colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, a solvent, an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator, and can be further used within a range that does not impair the effects of the present invention. Contains other ingredients. Hereinafter, the components contained in the photosensitive colored resin composition for color filters of the present invention will be described. The dispersant, color material, and solvent are the same as those described in the color material dispersion liquid of the present invention. , So the description here is omitted.

<鹼可溶性樹脂> <Alkali-soluble resin>

本發明中之鹼可溶性樹脂係具有酸性基者,作為黏合劑樹脂發揮作用,且可自於圖案形成時使用之鹼性顯影液中可溶性者中適當選擇而使用。於本發明中,所謂鹼可溶性樹脂,可將酸值為40mgKOH/g以上作為標準。本發明中之較佳之鹼可溶性樹脂係具有酸性基、通常具有羧基之樹脂,具體而言,可列舉:具有羧基之丙烯酸系共聚合體及具有羧基之苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂、具有羧基之環氧(甲基)丙烯酸酯樹脂等。該等中尤佳者係於側鏈具有羧基並且進而於側鏈具有乙烯性不飽和基等光聚合性官能基者。其原因在於,藉由含有光聚合性官能基,所形成之硬化膜之膜強度提高。又,該等丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂、以及環氧丙烯酸酯樹脂亦可混合2種以上而使用。 The alkali-soluble resin in the present invention has an acidic group, functions as a binder resin, and can be appropriately selected and used from those that are soluble in the alkaline developer used for pattern formation. In the present invention, the so-called alkali-soluble resin may have an acid value of 40 mgKOH/g or more as a standard. Preferred alkali-soluble resins in the present invention are resins having acidic groups and usually having carboxyl groups. Specifically, acrylic resins such as acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups, Epoxy (meth)acrylate resin with carboxyl group, etc. Among these, particularly preferable ones are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. The reason is that the film strength of the formed cured film is improved by containing the photopolymerizable functional group. In addition, acrylic resins such as these acrylic copolymers and styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination of two or more types.

包含具有羧基之構成單元之丙烯酸系共聚合體、及具有羧基之苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂例如為藉由公知方法使含羧基之乙烯系不飽和單體、及視需要能夠進行共聚合之其他單體進行(共)聚合而獲得之(共)聚合體。作為含羧基之乙烯系不飽和單體,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、衣康酸、丁烯酸、桂皮酸、丙烯酸二聚物等。又,亦可利用(甲基)丙烯酸2-羥基乙酯等具有羥基之單體與如順丁烯二酸酐或酞酸酐、環己烷二羧酸酐之環狀 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、衣康酸酐、檸康酸酐等含酸酐之單體作為羧基之前驅物。其中,就共聚合性或成本、溶解性、玻璃轉移溫度等之方面而言,尤佳為(甲基)丙烯酸。 Acrylic resins such as acrylic copolymers containing structural units having a carboxyl group and styrene-acrylic copolymers having a carboxyl group are, for example, carboxyl-containing ethylenically unsaturated monomers that can be copolymerized by a known method. A (co)polymer obtained by (co)polymerizing other polymerized monomers. Examples of carboxyl group-containing ethylenically unsaturated monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate, fumaric acid, and itaconic acid. Acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. In addition, the addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω- Carboxy-polycaprolactone mono(meth)acrylate and the like. In addition, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as the carboxyl group precursor. Among them, (meth)acrylic acid is particularly preferred in terms of copolymerization, cost, solubility, glass transition temperature, and the like.

就著色層之密接性優異之方面而言,鹼可溶性樹脂較佳為進而具有烴環。獲得如下見解:藉由於鹼可溶性樹脂中具有作為體積大之基之烴環,所獲得之著色層具有耐溶劑性,尤其可抑制著色層之膨潤。關於作用雖不明確,但推斷藉由於著色層內含有體積大之烴環,而抑制著色層內之分子之移動,結果塗膜之強度變高,抑制由溶劑所引起之膨潤。作為此種烴環,可列舉可具有取代基之環狀脂肪族烴環、可具有取代基之芳香族環、及該等之組合,烴環亦可具有羰基、羧基、氧基羰基、醯胺基等取代基。其中,於含有脂肪族環之情況下,著色層之耐熱性或密接性提高,並且所獲得之著色層之亮度提高。作為烴環之具體例,可列舉:環丙烷、環丁烷、環戊烷、環己烷、降

Figure 107106607-A0101-12-0052-37
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、茀等芳香族環;聯苯、聯三苯、二苯基甲烷、三苯基甲烷、茋等鏈狀多環或下述化學式(ii)所示之Cardo構造等。 In terms of excellent adhesion of the colored layer, the alkali-soluble resin preferably further has a hydrocarbon ring. It was found that the coloring layer obtained has solvent resistance due to the hydrocarbon ring as a bulky group in the alkali-soluble resin, and especially the swelling of the coloring layer can be suppressed. Although the effect is not clear, it is inferred that the coloring layer contains a large hydrocarbon ring and inhibits the movement of molecules in the coloring layer. As a result, the strength of the coating film becomes higher and the swelling caused by the solvent is suppressed. Examples of such a hydrocarbon ring include a cycloaliphatic hydrocarbon ring that may have a substituent, an aromatic ring that may have a substituent, and combinations of these. The hydrocarbon ring may also have a carbonyl group, a carboxyl group, an oxycarbonyl group, and an amide group. Substituents such as groups. Among them, in the case of containing an aliphatic ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved. Specific examples of the hydrocarbon ring include: cyclopropane, cyclobutane, cyclopentane, cyclohexane,
Figure 107106607-A0101-12-0052-37
Alkanes, tricyclic [5.2.1.0(2,6)] decane (dicyclopentane), adamantane and other aliphatic hydrocarbon rings; benzene, naphthalene, anthracene, phenanthrene, sulphur and other aromatic rings; biphenyl, dicyclopentane Chain polycyclic rings such as benzene, diphenylmethane, triphenylmethane, stilbene, or the Cardo structure shown in the following chemical formula (ii), etc.

Figure 107106607-A0101-12-0052-14
Figure 107106607-A0101-12-0052-14

又,鹼可溶性樹脂亦較佳為具有下述通式(iii)所表示之順丁烯二醯亞胺構造。 In addition, the alkali-soluble resin also preferably has a maleimide structure represented by the following general formula (iii).

Figure 107106607-A0101-12-0053-15
Figure 107106607-A0101-12-0053-15

(於通式(iii)中,RM為可經取代之烴環。) (In the general formula (iii), R M is a substituted hydrocarbon ring.)

於鹼可溶性樹脂具有上述通式(iii)所表示之順丁烯二醯亞胺構造之情況下,由於烴環具有氮原子,故而與本發明之分散劑之相溶性極佳,顯影殘渣之抑制效果提高。作為上述通式(iii)之RM中之可經取代之烴環之具體例,可列舉與上述烴環之具體例相同者。 When the alkali-soluble resin has the maleimide structure represented by the above general formula (iii), since the hydrocarbon ring has a nitrogen atom, it has excellent compatibility with the dispersant of the present invention and suppresses development residue The effect is improved. As specific examples of the hydrocarbon ring which may be substituted in R M of the above general formula (iii), the same as the specific examples of the above hydrocarbon ring can be cited.

於含有脂肪族環作為烴環之情況下,著色層之耐熱性或密接性提高,並且所獲得之著色層之亮度提高,就該方面而言較佳。又,於包含上述化學式(ii)所示之Cardo構造之情況下,著色層之硬化性提高,耐溶劑性(NMP膨潤抑制)提高,就該方面而言尤佳。 In the case of containing an aliphatic ring as a hydrocarbon ring, the heat resistance or adhesion of the colored layer is improved, and the brightness of the obtained colored layer is improved, which is preferable in this respect. In addition, when the Cardo structure represented by the above chemical formula (ii) is included, the hardenability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable in this respect.

於本發明中使用之鹼可溶性樹脂中,使用包含與具有羧基之構成單元不同之具有上述烴環之構成單元之丙烯酸系共聚合體易於調整各構成單元量,增加具有上述烴環之構成單元量而易於使該構成單元所具有之功能提高,就該方面而言較佳。包含具有羧基之構成單元與上述烴環之丙烯酸系共聚合體可藉由使用具有烴環之乙烯系不飽和單體作為上述「能夠共聚合之其他單體」而製備。作為上述具有烴環之乙烯系不飽和單體,例如可列舉:(甲基) 丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸異

Figure 107106607-A0101-12-0054-38
酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯等,就於加熱處理中亦維持顯影後之著色層之剖面形狀之效果較大之方面而言,較佳為(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸金剛烷基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、苯乙烯,尤佳為苯乙烯。又,就顯影殘渣之抑制效果之方面而言,作為上述具有烴環之乙烯系不飽和單體,較佳為具有上述順丁烯二醯亞胺構造之單體,較佳為苯乙烯,尤佳為苯乙烯。 In the alkali-soluble resin used in the present invention, the use of an acrylic copolymer containing the structural unit having the above-mentioned hydrocarbon ring different from the structural unit having a carboxyl group makes it easy to adjust the amount of each structural unit and increase the amount of the structural unit having the above-mentioned hydrocarbon ring. It is easy to improve the function of the constituent unit, which is preferable in this respect. The acrylic copolymer containing a structural unit having a carboxyl group and the above-mentioned hydrocarbon ring can be prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other monomer capable of copolymerization". As the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring, for example, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, (meth) Acrylic Iso
Figure 107106607-A0101-12-0054-38
Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, etc., are more effective in maintaining the cross-sectional shape of the colored layer after development during heat treatment. Preferred are cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, Styrene is particularly preferably styrene. Also, in terms of the effect of suppressing development residues, as the above-mentioned ethylenically unsaturated monomer having a hydrocarbon ring, a monomer having the above-mentioned maleimide structure is preferred, and styrene is preferred, and particularly It is preferably styrene.

又,本發明所使用之鹼可溶性樹脂較佳為於側鏈具有乙烯系雙鍵。於具有乙烯系雙鍵之情況下,於彩色濾光片製造時之樹脂組成物之硬化步驟中,該鹼可溶性樹脂與上述本發明之分散劑可形成交聯鍵,又,該鹼可溶性樹脂彼此、或該鹼可溶性樹脂與光聚合性化合物等可形成交聯鍵。因此,若將於側鏈具有乙烯系雙鍵之鹼可溶性樹脂與本發明之分散劑組合而使用,則藉由協同效應而進一步提高硬化膜之膜強度,因此可進一步提高著色層之亮度及ITO膜之龜裂性,進而提高耐顯影性,又,抑制硬化膜之熱收縮而使其與基板之密接性變得優異。於鹼可溶性樹脂中導入乙烯系雙鍵之方法只要自習知公知之方法中適當選擇即可。例如可列舉:使分子內一併具有環氧基與乙烯系雙鍵之化合物、例如(甲基)丙烯酸縮水甘油酯等與鹼可溶性樹脂所具有之羧基進行加成,而對側鏈導入乙烯系雙鍵之方法;或預先將具有羥基之構成單元導入至共聚合體中,使其與於分子內具備異氰酸基及乙烯系雙鍵之化合物進行加成,而對側鏈導入乙烯系雙鍵之方法等。 In addition, the alkali-soluble resin used in the present invention preferably has an ethylene-based double bond in the side chain. In the case of having an ethylene-based double bond, the alkali-soluble resin and the dispersant of the present invention can form a cross-linked bond during the curing step of the resin composition when the color filter is manufactured, and the alkali-soluble resin is mutually Or the alkali-soluble resin and the photopolymerizable compound may form a crosslinked bond. Therefore, if an alkali-soluble resin having an ethylene-based double bond in the side chain is used in combination with the dispersant of the present invention, the film strength of the cured film will be further improved by a synergistic effect, and the brightness of the colored layer and ITO can be further improved The cracking property of the film further improves the development resistance, and the heat shrinkage of the cured film is suppressed to make it excellent in adhesion to the substrate. The method of introducing the ethylene-based double bond into the alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a compound having an epoxy group and a vinyl double bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of an alkali-soluble resin, and the vinyl group is introduced into the side chain. Double bond method; or introduce the structural unit with hydroxyl group into the copolymer in advance, make it add to the compound with isocyanate group and ethylene double bond in the molecule, and introduce ethylene double bond to the side chain The method and so on.

本發明中使用之鹼可溶性樹脂亦可進而含有(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等、具有酯基之構成單元等其他構成單元。具有酯基之構成單元不僅作為抑制彩色濾光片用感光性著色樹脂組成物之鹼可溶性之成分發揮功能,而且亦作為提高對溶劑之溶解性、進而提高溶劑再溶解性之成分發揮功能。 The alkali-soluble resin used in the present invention may further contain other structural units such as methyl (meth)acrylate, ethyl (meth)acrylate, etc., structural units having an ester group. The structural unit having an ester group not only functions as a component that suppresses the alkali solubility of the photosensitive colored resin composition for color filters, but also functions as a component that improves solubility in solvents and further improves solvent resolubility.

本發明中使用之鹼可溶性樹脂較佳為包含具有羧基之構成單元及具有烴環之構成單元之丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂,更佳為包含具有羧基之構成單元、具有烴環之構成單元及具有乙烯系雙鍵之構成單元的丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂。 The alkali-soluble resin used in the present invention preferably includes acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having a carboxyl group and structural units having a hydrocarbon ring, and more preferably includes a structure having a carboxyl group Acrylic resins such as units, structural units having a hydrocarbon ring, and structural units having a vinyl double bond, and acrylic resins such as styrene-acrylic copolymers.

鹼可溶性樹脂可藉由適當調整各構成單元之饋入量而成為具有所期望之性能之鹼可溶性樹脂。 The alkali-soluble resin can be made into an alkali-soluble resin with desired performance by appropriately adjusting the feeding amount of each constituent unit.

就獲得良好之圖案之方面而言,含羧基之乙烯系不飽和單體之饋入量較佳為相對於單體總量為5質量%以上,更佳為10質量%以上。另一方面,就抑制顯影後之圖案表面之膜粗糙等之方面而言,含羧基之乙烯系不飽和單體之饋入量較佳為相對於單體總量為50質量%以下,更佳為40質量%以下。若含羧基之乙烯系不飽和單體之比率為上述下限值以上,則所獲得之塗膜之對鹼性顯影液之溶解性充分,又,若含羧基之乙烯系不飽和單體之比率為上述上限值以下,則有於利用鹼性顯影液進行之顯影時不易產生所形成之圖案自基板之脫落或圖案表面之膜粗糙之傾向。 In terms of obtaining a good pattern, the feeding amount of the carboxyl group-containing ethylenically unsaturated monomer is preferably 5% by mass or more, and more preferably 10% by mass or more with respect to the total amount of monomers. On the other hand, in terms of suppressing film roughness on the pattern surface after development, etc., the feeding amount of the carboxyl-containing ethylenic unsaturated monomer is preferably 50% by mass or less relative to the total amount of monomers, and more preferably It is 40% by mass or less. If the ratio of the carboxyl group-containing ethylenically unsaturated monomer is more than the above lower limit, the obtained coating film will have sufficient solubility in alkaline developer, and if the ratio of the carboxyl group-containing ethylenically unsaturated monomer is When the value is below the above upper limit, it tends to be difficult to cause the formed pattern to fall off from the substrate or the film on the surface of the pattern is rough during development using an alkaline developer.

又,於作為鹼可溶性樹脂更佳地使用之包含具有乙烯性雙鍵之構成單元之丙烯酸系共聚合體及苯乙烯-丙烯酸系共聚合體等丙烯酸系樹脂中,一併具有環氧基與乙烯系雙鍵之化合物較佳 為相對於含羧基之乙烯系不飽和單體之饋入量為10質量%~95質量%,更佳為15質量%~90質量%。 In addition, in acrylic resins such as acrylic copolymers and styrene-acrylic copolymers containing structural units having ethylenic double bonds, which are more preferably used as alkali-soluble resins, they have both epoxy groups and vinyl double bonds. The compound of the bond is preferably 10% by mass to 95% by mass, and more preferably 15% by mass to 90% by mass relative to the feeding amount of the carboxyl-containing ethylenically unsaturated monomer.

含羧基之共聚合體之較佳之重量平均分子量(Mw)較佳為1,000~50,000之範圍,進而較佳為3,000~20,000。若未滿1,000,則有硬化後之黏合劑功能顯著降低之情況,若超過50,000,則有於利用鹼性顯影液進行顯影時難以形成圖案之情況。再者,含羧基之共聚合體之上述重量平均分子量(Mw)可將聚苯乙烯作為標準物質,將THF作為洗提液,藉由Shodex GPC System-21H進行測定。 The preferred weight average molecular weight (Mw) of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 50,000, and more preferably 3,000 to 20,000. If it is less than 1,000, the adhesive function after curing may be significantly reduced, and if it exceeds 50,000, it may be difficult to form a pattern during development with an alkaline developer. Furthermore, the above-mentioned weight average molecular weight (Mw) of the carboxyl group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.

作為具有羧基之環氧(甲基)丙烯酸酯樹脂,並無特別限定,適宜為使環氧化合物和含不飽和基之單羧酸之反應物與酸酐反應而獲得之環氧(甲基)丙烯酸酯化合物。環氧化合物、含不飽和基之單羧酸及酸酐可自公知者中適當選擇而使用。具有羧基之環氧(甲基)丙烯酸酯樹脂可分別單獨使用1種,亦可併用兩種以上。 The epoxy (meth)acrylate resin having a carboxyl group is not particularly limited, and it is preferably an epoxy (meth)acrylic acid obtained by reacting a reactant of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride Ester compound. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. The epoxy (meth)acrylate resin which has a carboxyl group may be used individually by 1 type, respectively, and may use 2 or more types together.

關於鹼可溶性樹脂,就對用於顯影液之鹼性水溶液之顯影性(溶解性)之方面而言,較佳為選擇酸值為50mgKOH/g以上者而使用。關於鹼可溶性樹脂,就對用於顯影液之鹼性水溶液之顯影性(溶解性)之方面、及對基板之密接性之方面而言,較佳為酸值為70mgKOH/g以上且300mgKOH/g以下,其中較佳為70mgKOH/g以上且280mgKOH/g以下。再者,鹼可溶性樹脂之酸值可依照JIS K 0070:1992進行測定。 Regarding the alkali-soluble resin, it is preferable to select one having an acid value of 50 mgKOH/g or more in terms of the developability (solubility) of the alkaline aqueous solution used in the developer. Regarding the alkali-soluble resin, it is preferable that the acid value is 70 mgKOH/g or more and 300 mgKOH/g in terms of the developability (solubility) to the alkaline aqueous solution used in the developer and the adhesion to the substrate. Hereinafter, among them, it is preferably 70 mgKOH/g or more and 280 mgKOH/g or less. Furthermore, the acid value of the alkali-soluble resin can be measured in accordance with JIS K 0070:1992.

就獲得硬化膜之膜強度提高而耐顯影性提高,與基板之密接性優異之效果之方面而言,於鹼可溶性樹脂之側鏈具有乙烯系不飽和基之情況下之乙烯系不飽和鍵當量較佳為100~2000之範 圍,尤佳為140~1500之範圍。若該乙烯系不飽和鍵當量為100以上,則耐顯影性或密接性優異。又,若為2000以下,則可相對增加上述具有羧基之構成單元或具有烴環之構成單元等其他構成單元之比率,因此顯影性或耐熱性優異。又,就與上述分散劑組合時之協同效應優異,進一步提高著色層之亮度及ITO耐龜裂性之方面而言,較佳為上述分散劑中之於鹽形成前之嵌段共聚合體中之側鏈所含之(甲基)丙烯醯基當量為上述較佳之範圍,且鹼可溶性樹脂之該乙烯系不飽和鍵當量為上述較佳之範圍。此處,所謂乙烯系不飽和鍵當量係上述鹼可溶性樹脂中之乙烯系不飽和鍵每1莫耳之重量平均分子量,以下述數式(2)表示。 In terms of the effect of improving the film strength of the cured film and improving the development resistance, and the excellent adhesion to the substrate, the equivalent of the ethylenic unsaturated bond when the side chain of the alkali-soluble resin has an ethylenic unsaturated group It is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylene-based unsaturated bond equivalent is 100 or more, the development resistance or adhesion is excellent. In addition, if it is 2000 or less, the ratio of other structural units such as the structural unit having a carboxyl group or the structural unit having a hydrocarbon ring can be relatively increased, and therefore the developability and heat resistance are excellent. In addition, in terms of the excellent synergistic effect when combined with the above-mentioned dispersing agent, further improving the brightness of the colored layer and the ITO crack resistance, the above-mentioned dispersing agent is preferably the one in the block copolymer before salt formation. The (meth)acrylic acid group equivalent contained in the side chain is in the above-mentioned preferable range, and the ethylene-based unsaturated bond equivalent of the alkali-soluble resin is in the above-mentioned preferable range. Here, the ethylene-based unsaturated bond equivalent is the weight average molecular weight per mole of the ethylene-based unsaturated bond in the alkali-soluble resin, and is represented by the following formula (2).

數式(2) 乙烯系不飽和鍵當量(g/mol)=W(g)/M(mol) Formula (2) Ethylene unsaturated bond equivalent (g/mol)=W(g)/M(mol)

(數式(2)中,W表示鹼可溶性樹脂之質量(g),M表示鹼可溶性樹脂W(g)中所含之乙烯系雙鍵之莫耳數(mol)) (In the formula (2), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of the ethylene double bond contained in the alkali-soluble resin W(g))

上述乙烯系不飽和鍵當量例如亦可藉由依據JIS K 0070:1992所記載之碘值之試驗方法,測定鹼可溶性樹脂每1g中所含之乙烯系雙鍵之數量而算出。 The above-mentioned ethylene-based unsaturated bond equivalent can also be calculated by measuring the number of ethylene-based double bonds per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992, for example.

彩色濾光片用感光性著色樹脂組成物中所使用之鹼可溶性樹脂可單獨使用1種,亦可組合2種以上而使用,作為其含量,並無特別限制,相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量,鹼可溶性樹脂較佳為5質量%~60質量%,進而較佳為10質量%~40質量%之範圍內。若鹼可溶性樹脂之含量為上述下限值以上,則可獲得充分之鹼顯影性,又,若鹼可溶性樹脂之含量為上述上限值以下,則可於顯影時抑制膜粗糙或圖案之缺 損。 The alkali-soluble resin used in the photosensitive colored resin composition for color filters may be used singly or in combination of two or more. There is no particular limitation on the content thereof. Compared to photosensitive color filters for color filters, the alkali-soluble resin may be used alone or in combination. The total amount of solid content of the colored resin composition, the alkali-soluble resin is preferably 5% by mass to 60% by mass, and more preferably in the range of 10% by mass to 40% by mass. If the content of the alkali-soluble resin is more than the above lower limit, sufficient alkali developability can be obtained, and if the content of the alkali-soluble resin is less than the above upper limit, film roughness or pattern defects can be suppressed during development.

<多官能單體> <Multifunctional monomer>

彩色濾光片用感光性著色樹脂組成物中所使用之多官能單體只要為能夠藉由下述光起始劑進行聚合者即可,並無特別限定,通常使用具有2個以上之乙烯系不飽和雙鍵之化合物,尤佳為具有2個以上之丙烯醯基或甲基丙烯醯基之多官能(甲基)丙烯酸酯。作為此種多官能(甲基)丙烯酸酯,只要自習知公知者中適當選擇而使用即可。作為具體例,例如可列舉日本專利特開2013-029832號公報所記載者等。 The polyfunctional monomer used in the photosensitive colored resin composition for color filters is not particularly limited as long as it can be polymerized by the following photoinitiator. Generally, an ethylene-based monomer having two or more monomers is used. The compound with an unsaturated double bond is particularly preferably a multifunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups. As such a polyfunctional (meth)acrylate, what is necessary is just to select it suitably from a well-known well-known thing, and use. As a specific example, for example, those described in JP 2013-029832 A, etc. can be cited.

該等多官能(甲基)丙烯酸酯只要單獨使用1種即可,亦可組合2種以上而使用。又,於對本發明之彩色濾光片用感光性著色樹脂組成物要求優異之光硬化性(高感度)之情況下,多官能單體較佳為具有3個(三官能)以上之能夠聚合之雙鍵者,較佳為三元以上之多元醇之聚(甲基)丙烯酸酯類或其等之二羧酸改質物,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質物、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質物、二季戊四醇六(甲基)丙烯酸酯等。於彩色濾光片用感光性著色樹脂組成物中使用之上述多官能單體之含量並無特別限制,相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量,多官能單體較佳為5~60質量%,進而較佳為10~40質量%之範圍內。若多官能單體之含量少於上述下限值,則無法充分地進行光硬化,有曝光部分於 顯影時溶出之情況,又,若多官能單體之含量多於上述上限值,則有鹼顯影性降低之虞。 These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the photosensitive colored resin composition for color filters of the present invention is required to have excellent photocuring properties (high sensitivity), it is preferable that the multifunctional monomer has three (trifunctional) or more polymerizable monomers. Double bonds are preferably poly(meth)acrylates of trivalent or higher polyols or their dicarboxylic acid modifiers. Specifically, trimethylolpropane tri(meth)acrylic acid is preferred Esters, pentaerythritol tri(meth)acrylate, succinic acid modification product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Acrylate, succinic acid modification of dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. The content of the above-mentioned polyfunctional monomer used in the photosensitive colored resin composition for color filters is not particularly limited, and the polyfunctional monofunctional monomer is relative to the total solid content of the photosensitive colored resin composition for color filters. The body is preferably 5-60% by mass, and more preferably within the range of 10-40% by mass. If the content of the multifunctional monomer is less than the above lower limit, the photocuring cannot be carried out sufficiently, and the exposed part may be eluted during development, and if the content of the multifunctional monomer is more than the above upper limit, there will be The alkali developability may decrease.

<光起始劑> <Photoinitiator>

作為本發明之彩色濾光片用著色樹脂組成物中所使用之光起始劑,並無特別限制,可自習知已知之各種起始劑中使用1種或組合2種以上而使用。作為光起始劑,可列舉:芳香族酮類、安息香醚類、鹵甲基

Figure 107106607-A0101-12-0059-39
二唑化合物、α-胺基酮、聯咪唑類、N,N-二甲胺基二苯甲酮、鹵甲基-S-三
Figure 107106607-A0101-12-0059-40
系化合物、9-氧硫
Figure 107106607-A0101-12-0059-41
等。作為光起始劑之具體例,可列舉:二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮等芳香族酮類、安息香甲醚等安息香醚類、乙基安息香等安息香、2-(鄰氯苯基)-4,5-苯基咪唑二聚物等雙咪唑類、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-
Figure 107106607-A0101-12-0059-42
二唑等鹵甲基
Figure 107106607-A0101-12-0059-43
二唑化合物、2-(4-丁氧基-萘-1-基)-4,6-雙-三氯甲基-S-三
Figure 107106607-A0101-12-0059-44
等鹵甲基-S-三
Figure 107106607-A0101-12-0059-45
系化合物、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 107106607-A0101-12-0059-46
啉基丙酮、1,2-苄基-2-二甲胺基-1-(4-
Figure 107106607-A0101-12-0059-47
啉基苯基)-丁酮-1,1-羥基-環己基-苯基酮、二苯基乙二酮、苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚、聯苯醯二甲基縮酮、二甲胺基苯甲酸酯、對二甲胺基苯甲酸異戊酯、2-正丁氧基乙基-4-二甲胺基苯甲酸酯、2-氯-9-氧硫
Figure 107106607-A0101-12-0059-48
、2,4-二乙基-9-氧硫
Figure 107106607-A0101-12-0059-49
、2,4-二甲基-9-氧硫
Figure 107106607-A0101-12-0059-50
、異丙基-9-氧硫
Figure 107106607-A0101-12-0059-51
、4-苯甲醯基-甲基二苯硫醚、1-羥基-環己基-苯基酮、2-苄基-2-(二甲胺基)-1-[4-(4-
Figure 107106607-A0101-12-0059-52
啉基)苯基]-1-丁酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-
Figure 107106607-A0101-12-0059-53
啉基)苯基]-1-丁酮、α-二甲氧基-α-苯基苯乙酮、苯基 雙(2,4,6-三甲基苯甲醯基)氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-(4-
Figure 107106607-A0101-12-0060-54
啉基)-1-丙酮等。其中,較佳為使用2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 107106607-A0101-12-0060-55
啉基丙烷-1-酮、2-苄基-2-(二甲胺基)-1-(4-
Figure 107106607-A0101-12-0060-56
啉基苯基)-1-丁酮、4,4'-雙(二乙胺基)二苯甲酮、二乙基-9-氧硫
Figure 107106607-A0101-12-0060-57
。進而,就感度調整、抑制滲水、提高耐顯影性之方面而言,較佳為將如2-甲基-1-[4-(甲硫基)苯基]-2-
Figure 107106607-A0101-12-0060-58
啉基丙烷-1-酮之α-胺基苯乙酮系起始劑與如二乙基-9-氧硫
Figure 107106607-A0101-12-0060-59
之9-氧硫
Figure 107106607-A0101-12-0060-60
系起始劑組合。使用α-胺基苯乙酮系起始劑與9-氧硫
Figure 107106607-A0101-12-0060-61
系起始劑之情況下之該等之合計含量相對於著色樹脂組成物之固形物成分總量,較佳為5質量%~15質量%。若起始劑量為15質量%以下,則製造製程中之昇華物減少,因此較佳。若起始劑量為5質量%以上,則滲水等耐顯影性提高。 The photoinitiator used in the colored resin composition for the color filter of the present invention is not particularly limited, and it can be used alone or in combination of two or more of various known initiators. Examples of photoinitiators include aromatic ketones, benzoin ethers, and halomethyl
Figure 107106607-A0101-12-0059-39
Diazole compounds, α-amino ketones, biimidazoles, N,N-dimethylamino benzophenone, halomethyl-S-tri
Figure 107106607-A0101-12-0059-40
Series compounds, 9-oxysulfur
Figure 107106607-A0101-12-0059-41
Wait. Specific examples of the photoinitiator include benzophenone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Aromatic ketones, benzoin ethers such as methyl benzoin, benzoin such as ethyl benzoin, bisimidazoles such as 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-trichloromethyl- 5-(p-methoxystyryl)-1,3,4-
Figure 107106607-A0101-12-0059-42
Halomethyl
Figure 107106607-A0101-12-0059-43
Diazole compound, 2-(4-butoxy-naphthalene-1-yl)-4,6-bis-trichloromethyl-S-tri
Figure 107106607-A0101-12-0059-44
Isohalomethyl-S-tri
Figure 107106607-A0101-12-0059-45
Series compound, 2,2-Dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 107106607-A0101-12-0059-46
Alkylacetone, 1,2-benzyl-2-dimethylamino-1-(4-
Figure 107106607-A0101-12-0059-47
(Hydroxyphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenyl ethylenedione, benzyl benzoic acid, benzyl benzoic acid, methyl benzyl benzoate, 4-benzyl- 4'-Methyl diphenyl sulfide, biphenyl dimethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4- Dimethylaminobenzoate, 2-chloro-9-oxysulfur
Figure 107106607-A0101-12-0059-48
, 2,4-Diethyl-9-oxysulfur
Figure 107106607-A0101-12-0059-49
, 2,4-Dimethyl-9-oxysulfur
Figure 107106607-A0101-12-0059-50
, Isopropyl-9-oxysulfur
Figure 107106607-A0101-12-0059-51
, 4-Benzyl-methyl diphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-
Figure 107106607-A0101-12-0059-52
Linyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-
Figure 107106607-A0101-12-0059-53
(Hydroxy)phenyl)-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl) phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4-
Figure 107106607-A0101-12-0060-54
(Alpinyl)-1-acetone and the like. Among them, it is preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 107106607-A0101-12-0060-55
Linylpropan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-
Figure 107106607-A0101-12-0060-56
(Hydroxyphenyl)-1-butanone, 4,4'-bis(diethylamino)benzophenone, diethyl-9-oxysulfur
Figure 107106607-A0101-12-0060-57
. Furthermore, in terms of sensitivity adjustment, suppression of water seepage, and improvement of development resistance, it is preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-
Figure 107106607-A0101-12-0060-58
Alpha-aminoacetophenone initiators of hydroxypropane-1-one and diethyl-9-oxysulfur
Figure 107106607-A0101-12-0060-59
Of 9-oxysulfur
Figure 107106607-A0101-12-0060-60
Department of initiator combination. Using α-aminoacetophenone-based initiator and 9-oxysulfur
Figure 107106607-A0101-12-0060-61
In the case of the initiator, the total content of these is preferably 5% by mass to 15% by mass relative to the total solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimation in the manufacturing process is reduced, which is preferable. If the starting dose is 5% by mass or more, the development resistance such as water penetration improves.

本發明中,光起始劑尤其就可提高感度之方面而言,較佳為含有肟酯系光起始劑。又,藉由使用肟酯系光起始劑,於形成細線圖案時可容易抑制面內之線寬之不均。進而,藉由使用肟酯系光起始劑,有殘膜率提高,滲水產生抑制效果提高之傾向。再者,所謂滲水係指若使用提高鹼顯影性之成分,則於鹼顯影後以純水沖洗後產生如滲水之痕跡。此種滲水於後烘烤後會消失,因此作為製品並無問題,但於顯影後在圖案化面之外觀檢查中會作為不均異常被檢測出,產生無法區分正常品與異常品之問題。因此,若於外觀檢查中降低檢查裝置之檢查感度,則結果引起最終之彩色濾光片製品之良率降低而成為問題。作為該肟酯系光起始劑,就減少由分解物所引起之彩色濾光片用著色樹脂組成物之污染或裝置之污染之方面而言,其中較佳為具有芳香環者,更佳為具有包含芳香環之縮合環者,進而較佳為具有包含苯環與雜環之縮合環。作為肟酯系光 起始劑,可自1,2-辛二酮-1-[4-(苯硫基)-、2-(O-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-(O-乙醯基肟)、日本專利特開2000-80068號公報、特開2001-233842號公報、特表2010-527339、特表2010-527338、特開2013-041153等所記載之肟酯系光起始劑中適當選擇。作為市售品,亦可使用Irgacure OXE-01、具有二苯基硫醚骨架之Adeka Arkls NCI-930、TR-PBG-345、具有咔唑骨架之TR-PBG-304、具有茀骨架之TR-PBG-365、具有二苯硫醚骨架之TR-PBG-3057(以上為常州強力電子新材料公司製造)等。尤其就亮度之方面而言,較佳為使用具有二苯基硫醚骨架或茀骨架之肟酯系光起始劑。又,就感度較高之方面而言,較佳為使用具有咔唑骨架之肟酯系光起始劑。又,併用2種以上之肟酯系光起始劑於容易提高亮度、殘膜率且滲水產生抑制效果較高之方面較佳。尤其,就亮度較高且耐熱性較高之方面而言,較佳為併用2種具有二苯硫醚骨架之肟酯系光起始劑或併用具有二苯硫醚骨架之肟酯系光起始劑與具有茀骨架之肟酯系光起始劑。又,就感度、亮度優異之方面而言,較佳為併用具有咔唑骨架之肟酯系光起始劑與具有茀骨架之肟酯系光起始劑或具有二苯硫醚之肟酯系光起始劑。 In the present invention, the photoinitiator preferably contains an oxime ester-based photoinitiator in terms of improving sensitivity. In addition, by using the oxime ester-based photoinitiator, the unevenness of the line width in the plane can be easily suppressed when the thin line pattern is formed. Furthermore, by using an oxime ester-based photoinitiator, there is a tendency that the residual film rate is increased and the effect of suppressing water seepage generation is improved. Furthermore, the so-called water seepage means that if a component that improves alkali developability is used, it will produce traces such as water seepage after being rinsed with pure water after alkali development. This kind of water seepage disappears after post-baking, so there is no problem as a product, but it will be detected as an uneven abnormality in the appearance inspection of the patterned surface after development, causing a problem that normal products and abnormal products cannot be distinguished. Therefore, if the inspection sensitivity of the inspection device is lowered during the appearance inspection, it will result in a decrease in the yield of the final color filter product, which becomes a problem. As the oxime ester-based photoinitiator, in terms of reducing pollution of the colored resin composition for color filters or device pollution caused by decomposition products, those having an aromatic ring are preferred, and those having an aromatic ring are more preferred. Those having a condensed ring containing an aromatic ring further preferably have a condensed ring containing a benzene ring and a heterocyclic ring. As the oxime ester-based photoinitiator, it can be selected from 1,2-octanedione-1-[4-(phenylthio)-, 2-(O-benzyloxime)], ethyl ketone, 1-[ 9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-, 1-(O-acetyloxime), Japanese Patent Laid-Open No. 2000-80068, Among the oxime ester-based photoinitiators described in JP 2001-233842, JP 2010-527339, JP 2010-527338, JP 2013-041153, etc., are appropriately selected. As commercially available products, Irgacure OXE-01, Adeka Arkls NCI-930 with a diphenyl sulfide skeleton, TR-PBG-345, TR-PBG-304 with a carbazole skeleton, and TR- with a pyridine skeleton can also be used. PBG-365, TR-PBG-3057 with a diphenyl sulfide skeleton (the above are manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), etc. Particularly in terms of brightness, it is preferable to use an oxime ester-based photoinitiator having a diphenyl sulfide skeleton or a sulphur skeleton. Moreover, in terms of high sensitivity, it is preferable to use an oxime ester-based photoinitiator having a carbazole skeleton. In addition, the combined use of two or more oxime ester-based photoinitiators is preferable in that it is easy to improve the brightness, the residual film rate, and the effect of suppressing the occurrence of water seepage is high. In particular, in terms of high brightness and high heat resistance, it is preferable to use two kinds of oxime ester photoinitiators having a diphenyl sulfide skeleton in combination or to use an oxime ester photoinitiator having a diphenyl sulfide skeleton in combination. Starter and oxime ester-based photoinitiator with citron skeleton. In addition, in terms of excellent sensitivity and brightness, it is preferable to use an oxime ester photoinitiator having a carbazole skeleton and an oxime ester photoinitiator having a pyridine skeleton or an oxime ester photoinitiator having a diphenyl sulfide in combination. Light initiator.

又,就抑制滲水且提高感度之方面而言,較佳為對肟酯系光起始劑組合具有三級胺構造之光起始劑而使用。其原因在於,具有三級胺構造之光起始劑於分子內具有作為氧淬滅劑之三級胺構造,因此自起始劑產生之自由基不易因氧而失活,可提高感度。作為上述具有三級胺構造之光起始劑之市售品,例如可列舉:2-甲基-1-(4-甲硫基苯基)-2-

Figure 107106607-A0101-12-0061-62
啉基丙烷-1-酮(例如Irgacure907, BASF公司製造)、2-苄基-2-(二甲胺基)-1-(4-
Figure 107106607-A0101-12-0062-63
啉基苯基)-1-丁酮(例如Irgacure369,BASF公司製造)、4,4'-雙(二乙胺基)二苯甲酮(例如HiCure ABP,川口藥品製造)等。又,對肟酯系光起始劑組合9-氧硫
Figure 107106607-A0101-12-0062-64
系起始劑就感度調整、抑制滲水、提高耐顯影性之方面而言較佳,將2種以上之肟酯系光起始劑與9-氧硫
Figure 107106607-A0101-12-0062-65
系起始劑組合就提高亮度、殘膜率、容易進行感度調整、抑制滲水產生之效果較高及提高耐顯影性之方面而言較佳。 Moreover, in terms of suppressing water seepage and improving sensitivity, it is preferable to use a photoinitiator having a tertiary amine structure in combination with an oxime ester-based photoinitiator. The reason is that a photoinitiator with a tertiary amine structure has a tertiary amine structure as an oxygen quencher in the molecule, so free radicals generated from the initiator are not easily deactivated by oxygen, and the sensitivity can be improved. As a commercially available product of the photoinitiator having the tertiary amine structure, for example, 2-methyl-1-(4-methylthiophenyl)-2-
Figure 107106607-A0101-12-0061-62
Alkylpropan-1-one (for example, Irgacure907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4-
Figure 107106607-A0101-12-0062-63
(Alolinylphenyl)-1-butanone (for example, Irgacure369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)benzophenone (for example, HiCure ABP, manufactured by Kawaguchi Pharmaceutical), and the like. In addition, 9-oxysulfur is combined with oxime ester-based photoinitiator
Figure 107106607-A0101-12-0062-64
The initiator is preferable in terms of sensitivity adjustment, suppression of water seepage, and improvement of development resistance. Two or more oxime ester-based photoinitiators and 9-oxysulfur
Figure 107106607-A0101-12-0062-65
The combination of initiators is preferable in terms of improving brightness, residual film rate, easy adjustment of sensitivity, high effect of suppressing water seepage, and improvement of development resistance.

本發明之彩色濾光片用著色樹脂組成物中所使用之光起始劑之含量相對於上述多官能單體100質量份,通常為0.01質量份~100質量份左右,較佳為5質量份~60質量份。若該含量為上述下限值以上,則充分地進行光硬化,抑制曝光部分於顯影時溶出,另一方面,若為上述上限值以下,則可抑制所獲得之著色層之黃變性變弱而導致之亮度降低。又,作為本發明之彩色濾光片用著色樹脂組成物中所使用之光起始劑,2種以上肟酯系光起始劑之合計含量相對於彩色濾光片用著色樹脂組成物之固形物成分總量為0.1質量%~12.0質量%、進而較佳為1.0質量%~8.0質量%之範圍內就充分地發揮該等光起始劑之併用效果之方面而言較佳。 The content of the photoinitiator used in the colored resin composition for color filters of the present invention is generally 0.01 to 100 parts by mass, preferably 5 parts by mass, relative to 100 parts by mass of the above-mentioned multifunctional monomer ~60 parts by mass. If the content is more than the above lower limit, the photohardening is sufficiently performed and the exposed part is prevented from eluting during development. On the other hand, if the content is less than the above upper limit, the yellowing of the obtained colored layer can be suppressed from becoming weak. The resulting brightness decreases. In addition, as the photoinitiator used in the colored resin composition for color filters of the present invention, the total content of two or more oxime ester-based photoinitiators is relative to the solid state of the colored resin composition for color filters It is preferable that the total amount of the material components is within the range of 0.1% by mass to 12.0% by mass, and more preferably 1.0% by mass to 8.0% by mass, in terms of sufficiently exhibiting the effect of the combined use of the photoinitiators.

關於本發明之彩色濾光片用著色樹脂組成物中使用之黏合劑成分,該等之合計含量相對於彩色濾光片用著色樹脂組成物之固形物成分總量,較佳為35質量%~97質量%,更佳為以40質量%~96質量%之比率調配。若為上述下限值以上,則可獲得硬度或與基板之密接性優異之著色層。又,若為上述上限值以下,則顯影性優異,亦抑制由熱收縮所引起之微小褶皺之產生。 Regarding the binder components used in the colored resin composition for color filters of the present invention, the total content of these relative to the total solid content of the colored resin composition for color filters is preferably 35% by mass~ 97% by mass, more preferably blended at a ratio of 40% to 96% by mass. If it is more than the above lower limit, a colored layer having excellent hardness and adhesion to the substrate can be obtained. In addition, if it is less than the above upper limit value, the developability is excellent, and the generation of fine wrinkles due to thermal shrinkage is also suppressed.

<抗氧化劑> <Antioxidant>

本發明之彩色濾光片用感光性著色樹脂組成物進而含有抗氧化劑就提高耐熱性、抑制色材之褪色及提高亮度之方面而言較佳。抗氧化劑只要自習知公知者中適當選擇即可。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,就耐熱性之方面而言,較佳為使用受阻酚系抗氧化劑。亦可為如國際公開第2014/021023號所記載之潛伏性抗氧化劑。 The photosensitive colored resin composition for a color filter of the present invention further contains an antioxidant in terms of improving heat resistance, suppressing color fading of the color material, and improving brightness. What is necessary is just to select an antioxidant suitably from a well-known thing. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, etc. In terms of heat resistance, it is preferable to use Hindered phenolic antioxidants. 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)、1,3,5-三(3,5-二第三丁基-4-羥基苄基)異氰尿酸酯(商品名:IRGANOX3114,BASF製造)、2,4,6-三(4-羥基-3,5-二第三丁基苄基)均三甲苯(商品名:IRGANOX1330,BASF製造)、2,2'-亞甲基雙(6-第三丁基-4-甲酚)(商品名:Sumilizer MDP-S,住友化學製造)、6,6'-硫代雙(2-第三丁基-4-甲酚)(商品名:IRGANOX1081,BASF製造)、3,5-二第三丁基-4-羥基苄基膦酸二乙酯(商品名:Irgamod 195,BASF製造)等。其中,就耐熱性及耐光性之方面而言,較佳為季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯](商品名:IRGANOX1010,BASF公司製造)。 Examples of hindered phenol-based antioxidants include: pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1, 3,5-Tris(3,5-Di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-Di-tert-butylbenzyl) mesitylene (trade name: IRGANOX1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX1081, manufactured by BASF), 3,5-di-tert-butyl Diethyl-4-hydroxybenzylphosphonate (trade name: Irgamod 195, manufactured by BASF) and the like. Among them, in terms of heat resistance and light resistance, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF Corporation manufacture).

本發明之彩色濾光片用感光性著色樹脂組成物若組合含有上述肟酯系光起始劑與抗氧化劑,則就藉由協同效應而使亮度提高之方面、殘膜率提高之方面、於形成細線圖案時直線性進一步提高、或如遮罩線寬之設計般形成細線圖案之能力提高之方面而言較佳。 If the photosensitive colored resin composition for a color filter of the present invention contains the above-mentioned oxime ester-based photoinitiator and antioxidant in combination, the synergistic effect will increase the brightness and increase the residual film rate. It is preferable in terms of the linearity is further improved when the thin line pattern is formed, or the ability to form the thin line pattern like the design of the mask line width is improved.

作為抗氧化劑之調配量,相對於著色樹脂組成物中之總固形物成分100質量份,抗氧化劑較佳為0.1質量份~10.0質量份,更佳為0.5質量份~5.0質量份。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,則可使本發明之著色樹脂組成物成為高感度之感光性樹脂組成物。 As the compounding amount of the antioxidant, relative to 100 parts by mass of the total solid content in the colored resin composition, the antioxidant is preferably 0.1 parts by mass to 10.0 parts by mass, more preferably 0.5 parts by mass to 5.0 parts by mass. 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 not more than the above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

於將抗氧化劑與上述肟酯系光起始劑組合使用之情況下,作為抗氧化劑之調配量,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~250質量份,更佳為3質量份~80質量份,進而更佳為5質量份~45質量份。若為上述範圍內,則上述組合之效果優異。 When an antioxidant is used in combination with the above-mentioned oxime ester-based photoinitiator, as the blending amount of the antioxidant, relative to 100 parts by mass of the total amount of the above-mentioned oxime-ester-based photoinitiator, the antioxidant is preferably 1 mass Parts to 250 parts by mass, more preferably 3 parts by mass to 80 parts by mass, and still more preferably 5 parts by mass to 45 parts by mass. If it is in the above range, the effect of the above combination is excellent.

<任意添加成分> <Optional ingredients>

於本發明之彩色濾光片用感光性著色樹脂組成物中,除上述抗氧化劑以外,亦可視需要含有各種添加劑。作為添加劑,例如可列舉:聚合終止劑、鏈轉移劑、調平劑、可塑劑、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。作為界面活性劑及可塑劑之具體例,例如可列舉日本專利特開2013-029832號公報所記載者。 In the photosensitive colored resin composition for color filters of the present invention, in addition to the above-mentioned antioxidant, various additives may be contained as needed. Examples of additives include polymerization terminator, chain transfer agent, leveling agent, plasticizer, surfactant, defoamer, silane coupling agent, ultraviolet absorber, adhesion promoter, and the like. As a specific example of a surfactant and a plasticizer, what is described in Unexamined-Japanese-Patent No. 2013-029832 can be mentioned, for example.

又,作為矽烷偶合劑,例如可列舉:KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-903、KBE-903、KBM573、KBM-403、KBE-402、KBE-403、KBM-303、KBM-802、KBM-803、KBE-9007、X-12-967C(Shin-Etsu Silicones公司製造)等。其中,就SiN基板之密接性之方面而言,較佳為具有甲基丙烯醯基、丙烯醯基之KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103。 Moreover, as the silane coupling agent, for example, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE -403, KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicones), etc. Among them, in terms of the adhesiveness of the SiN substrate, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 having a methacryl group and an acrylic group are preferable.

作為矽烷偶合劑之含量,相對於感光性著色樹脂組成物中之總固形物成分100質量份,矽烷偶合劑較佳為0.05質量份以上且10.0質量份以下,更佳為0.1質量份以上且5.0質量份以下。若為上述下限值以上且上述上限值以下,則基板密接性優異。 As the content of the silane coupling agent, relative to 100 parts by mass of the total solid content in the photosensitive colored resin composition, the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less, more preferably 0.1 parts by mass or more and 5.0 parts by mass. Parts by mass or less. If it is more than the said lower limit and less than the said upper limit, the board|substrate adhesiveness will be excellent.

<彩色濾光片用感光性著色樹脂組成物中之各成分之調配比率> <The blending ratio of the components in the photosensitive colored resin composition for color filters>

關於色材之合計含量,相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量,較佳為以3~65質量%、更佳為以4~60質量%之比率調配。若為上述下限值以上,則將彩色濾光片用感光性著色樹脂組成物塗佈為既定之膜厚(通常為1.0~5.0μm)時之著色層具有充分之色濃度。又,若為上述上限值以下,則可獲得保存穩定性優異並且具有充分之硬度或具有與基板之密接性之著色層。尤其於形成色材濃度較高之著色層之情況下,色材之含量相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量,較佳為以15~65質量%、更佳為以25~60質量%之比率調配。又,作為分散劑之含量,只要為可使色材均勻地分散者,則無特別限定,例如可以相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量為1~40質量%之比率使用。進而,較佳為相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總量以2~30質量%之比率調配,尤佳為以3~25質量%之比率調配。若為上述下限值以上,則色材之分散性及分散穩定性優異,彩色濾光片用感光性著色樹脂組成物之保存穩定性更優異。又,若為上述上限值以下,則顯影性變得良好。尤其於形成色材濃度較高之著色層之情況下,分散劑之含量相對於彩色濾光片用感光性著色樹脂組成物之固形物成分總 量,較佳為以2~25質量%、更佳為以3~20質量%之比率調配。再者,分散劑之質量於鹽型嵌段共聚合體之情況下為鹽形成前之上述嵌段共聚合體與有機酸化合物等之合計質量。又,溶劑之含量只要於可精度良好地形成著色層之範圍內適當設定即可。相對於含有該溶劑之彩色濾光片用感光性著色樹脂組成物之總量,通常較佳為55~95質量%之範圍內,其中更佳為65~88質量%之範圍內。藉由使上述溶劑之含量為上述範圍內,可成為塗佈性優異者。 The total content of the color materials is preferably 3 to 65% by mass, more preferably 4 to 60% by mass relative to the total solid content of the photosensitive colored resin composition for color filters. If it is more than the above lower limit, the colored layer has sufficient color density when the photosensitive colored resin composition for color filters is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, if it is less than the said upper limit, the coloring layer which is excellent in storage stability and has sufficient hardness or has adhesiveness with a board|substrate can be obtained. Especially in the case of forming a coloring layer with a high color material concentration, the content of the color material relative to the total solid content of the photosensitive coloring resin composition for color filters is preferably 15-65% by mass, and more It is better to mix at a ratio of 25-60% by mass. In addition, the content of the dispersant is not particularly limited as long as it can uniformly disperse the color material. For example, it can be 1-40 mass relative to the total solid content of the photosensitive colored resin composition for color filters. The ratio of% is used. Furthermore, it is preferable to mix|blend at the ratio of 2-30 mass% with respect to the total amount of the solid content of the photosensitive colored resin composition for color filters, and it is especially preferable to mix it at the ratio of 3-25 mass %. If it is more than the said lower limit, the dispersibility and dispersion stability of a color material will be excellent, and the storage stability of the photosensitive colored resin composition for color filters will be more excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially in the case of forming a coloring layer with a high color material concentration, the content of the dispersant relative to the total solid content of the photosensitive color resin composition for color filters is preferably 2-25% by mass, more It is better to mix with a ratio of 3-20% by mass. Furthermore, in the case of a salt-type block copolymer, the mass of the dispersant is the total mass of the block copolymer and the organic acid compound, etc. before the salt is formed. In addition, the content of the solvent may be appropriately set within a range in which the colored layer can be formed accurately. The total amount of the photosensitive colored resin composition for color filters containing the solvent is generally preferably in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. By making the content of the above-mentioned solvent within the above-mentioned range, it is possible to have excellent coatability.

<彩色濾光片用感光性著色樹脂組成物之製造方法> <Manufacturing Method of Photosensitive Colored Resin Composition for Color Filter>

本發明之彩色濾光片用感光性著色樹脂組成物之製造方法並無特別限定,例如可藉由於上述本發明之色材分散液中添加鹼可溶性樹脂、多官能單體、光起始劑及視需要之其他成分,並使用公知之混合方法進行混合而獲得。 The method for producing the photosensitive colored resin composition for color filters of the present invention is not particularly limited. For example, it can be achieved by adding alkali-soluble resin, polyfunctional monomer, photoinitiator, and the above-mentioned color material dispersion of the present invention. It can be obtained by mixing other ingredients as needed and using a well-known mixing method.

III.彩色濾光片 III. Color filter

本發明之彩色濾光片係至少具備基板及設置於該基板上之著色層者,且該著色層之至少一者為上述本發明之彩色濾光片用感光性著色樹脂組成物之硬化物。 The color filter of the present invention is provided with at least a substrate and a coloring layer provided on the substrate, and at least one of the coloring layers is a cured product of the photosensitive coloring resin composition for a color filter of the present invention.

參照圖對此種本發明之彩色濾光片進行說明。圖1係表示本發明之彩色濾光片之一例之概略剖面圖。根據圖1,本發明之彩色濾光片10具有基板1、遮光部2及著色層3。 The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light-shielding portion 2 and a coloring layer 3.

<著色層> <Colored layer>

本發明之彩色濾光片所使用之著色層係至少一者為上述本發 明之彩色濾光片用感光性著色樹脂組成物之硬化物之著色層。著色層通常形成於下述基板上之遮光部之開口部,通常包含3色以上之著色圖案。又,作為該著色層之排列,並無特別限定,例如可設為條紋型、馬賽克型、三角型、四像素配置型等一般之排列。又,著色層之寬度、面積等可任意地設定。該著色層之厚度係藉由調整塗佈方法、彩色濾光片用感光性著色樹脂組成物之固形物成分濃度或黏度等而適當控制,通常較佳為1~5μm之範圍。 At least one of the colored layers used in the color filter of the present invention is the colored layer of the cured product of the photosensitive colored resin composition for the color filter of the present invention. The colored layer is usually formed in the opening of the light-shielding portion on the following substrate, and usually contains a colored pattern of more than three colors. In addition, the arrangement of the colored layer is not particularly limited, and it can be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type. In addition, the width and area of the colored layer can be set arbitrarily. The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the photosensitive colored resin composition for color filters, and the like, and it is usually preferably in the range of 1 to 5 μm.

該著色層例如可藉由下述方法而形成。首先,使用噴霧塗佈法、浸漬塗佈法、棒式塗佈法、輥塗法、旋轉塗佈法、模嘴塗佈法等塗佈方法將上述本發明之彩色濾光片用感光性著色樹脂組成物塗佈於下述基板上,形成濕塗膜。其中,可較佳地使用旋轉塗佈法、模嘴塗佈法。繼而,使用加熱板或烘箱等使該濕塗膜乾燥後,介隔既定圖案之遮罩對其進行曝光,使鹼可溶性樹脂及多官能單體等進行光聚合反應而製成硬化塗膜。作為曝光所使用之光源,例如可列舉低壓水銀燈、高壓水銀燈、金屬鹵化物燈等紫外線、電子束等。曝光量係根據所使用之光源或塗膜之厚度等而適當調整。又,為了於曝光後促進聚合反應,亦可進行加熱處理。加熱條件係根據所使用之彩色濾光片用感光性著色樹脂組成物中之各成分之調配比率或塗膜之厚度等而適當選擇。 This colored layer can be formed by the following method, for example. First, use spray coating, dip coating, bar coating, roll coating, spin coating, die nozzle coating and other coating methods to color the above-mentioned photosensitive color filter of the present invention. The resin composition is applied on the following substrate to form a wet coating film. Among them, the spin coating method and the die nozzle coating method can be preferably used. Then, after the wet coating film is dried using a hot plate, an oven, etc., it is exposed through a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, etc. are subjected to a photopolymerization reaction to form a cured coating film. As a light source used for exposure, ultraviolet rays, electron beams, etc., such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, can be mentioned, for example. The amount of exposure is appropriately adjusted according to the light source used or the thickness of the coating film. In addition, in order to promote the polymerization reaction after exposure, heat treatment may also be performed. The heating conditions are appropriately selected according to the blending ratio of the components in the photosensitive colored resin composition for color filters used, the thickness of the coating film, and the like.

其次,藉由使用顯影液進行顯影處理,將未曝光部分溶解、去除,而以所期望之圖案形成塗膜。作為顯影液,通常使用使鹼溶解於水或水溶性溶劑中而成之溶液。亦可於該鹼性溶液中添加適量之界面活性劑等。又,顯影方法可採用一般之方法。於顯影處理後,通常進行顯影液之洗淨、彩色濾光片用感光性著色樹脂組 成物之硬化塗膜之乾燥而形成著色層。再者,於顯影處理後,亦可為了使塗膜充分地硬化而進行加熱處理。作為加熱條件,並無特別限定,根據塗膜之用途適當選擇。 Next, by performing a development process with a developer, the unexposed part is dissolved and removed, and a coating film is formed in a desired pattern. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. It is also possible to add an appropriate amount of surfactants and the like to the alkaline solution. In addition, general methods can be used for the development method. After the development process, the developer is usually washed, and the cured coating film of the photosensitive colored resin composition for color filters is dried to form a colored layer. In addition, after the development treatment, heat treatment may be performed in order to sufficiently harden the coating film. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.

<遮光部> <Shading part>

本發明之彩色濾光片中之遮光部係於下述基板上形成為圖案狀者,可與於一般之彩色濾光片中用作遮光部者相同。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。遮光部亦可為利用濺鍍法、真空蒸鍍法等所獲得之鉻等金屬薄膜。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之樹脂層。於含有遮光性粒子之樹脂層之情況下,有使用感光性抗蝕劑藉由顯影進行圖案化之方法、使用含有遮光性粒子之噴墨墨水進行圖案化之方法、將感光性抗蝕劑進行熱轉印之方法等。 The light-shielding part in the color filter of the present invention is formed in a pattern on the following substrate, which can be the same as the light-shielding part in a general color filter. The pattern shape of the light-shielding portion is not particularly limited, and examples include shapes such as a stripe shape and a matrix shape. The light-shielding part may also be a metal thin film such as chromium obtained by a sputtering method, a vacuum vapor deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin adhesive. In the case of a resin layer containing light-shielding particles, there are a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, and a photosensitive resist. Methods of thermal transfer, etc.

作為遮光部之膜厚,於金屬薄膜之情況下,設定為0.2~0.4μm左右,於為使黑色顏料分散或溶解於黏合劑樹脂中而成者之情況下,設定為0.5~2μm左右。 The film thickness of the light-shielding part is set to about 0.2~0.4μm in the case of a metal thin film, and is set to about 0.5~2μm when the black pigment is dispersed or dissolved in the binder resin.

<基板> <Substrate>

作為基板,係使用於下述透明基板、矽基板及於透明基板或矽基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。亦可於該等基板上形成其他彩色濾光片層、樹脂層、TFT等電晶體、電路等。作為本發明之彩色濾光片之透明基板,只要為對於可見光透明之基材即可,並無特別限定,可使用一般之彩色濾光片所使用之透明基板。 具體而言,可列舉:石英玻璃、無鹼玻璃、合成石英板等無可撓性之透明剛性材、或透明樹脂膜、光學用樹脂板、可撓性玻璃等具有可撓性之透明可撓性材。該透明基板之厚度並無特別限定,可根據本發明之彩色濾光片之用途而使用例如100μm~1mm左右者。再者,本發明之彩色濾光片亦可於上述基板、遮光部及著色層以外亦形成有例如外覆層或透明電極層、進而形成有配向膜或柱狀間隔件等。 As the substrate, it is used for the following transparent substrates, silicon substrates, and those having aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the transparent substrates or silicon substrates. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. can also be formed on these substrates. The transparent substrate of the color filter of the present invention is not particularly limited as long as it is a substrate transparent to visible light, and a transparent substrate used for general color filters can be used. Specifically, examples include: non-flexible transparent rigid materials such as quartz glass, alkali-free glass, synthetic quartz plates, or transparent resin films, optical resin plates, flexible glass, and other flexible transparent and flexible materials Sex material. The thickness of the transparent substrate is not particularly limited, and according to the use of the color filter of the present invention, for example, about 100 μm to 1 mm can be used. Furthermore, the color filter of the present invention may also be formed with, for example, an overcoat layer or a transparent electrode layer, and further an alignment film or columnar spacers, etc., besides the above-mentioned substrate, light-shielding portion, and coloring layer.

IV.顯示裝置 IV. Display device

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。本發明中,顯示裝置之構成並無特別限定,可自習知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。 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 it can be appropriately selected from conventionally known display devices. For example, a liquid crystal display device or an organic light-emitting display device can be cited.

[液晶顯示裝置] [Liquid crystal display device]

作為本發明之液晶顯示裝置,例如可列舉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之液晶顯示裝置。參照圖式對此種本發明之液晶顯示裝置進行說明。圖2係表示本發明之液晶表示裝置之一例之概略圖。如圖2所例示,本發明之液晶顯示裝置40具有彩色濾光片10、具有TFT陣列基板等之對向基板20及形成於上述彩色濾光片10與上述對向基板20之間之液晶層30。再者,本發明之液晶顯示裝置並不限定於該圖2所示之構成,可設為一般作為使用彩色濾光片之液晶顯示裝置公知之構成。 Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. The liquid crystal display device of the present invention will be described with reference to the drawings. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As shown in FIG. 2, the liquid crystal display device 40 of the present invention has a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer formed between the color filter 10 and the counter substrate 20 30. In addition, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2 and may be a configuration generally known as a liquid crystal display device using a color filter.

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,例如可列舉扭曲向列(TN,Twisted Nematic)方式、橫向電場效應顯示技術(IPS,In-plane Switching)方式、光學補償雙折射(OCB,Optically Compensated Birefringence)方式、及多域垂直配向(MVA,Multi-Domain Vertical Alignment)方式等。本發明中,該等中之任一方式均可較佳地使用。又,作為對向基板,可根據本發明之液晶顯示裝置之驅動方式等適當選擇而使用。進而,作為構成液晶層之液晶,可根據本發明之液晶顯示裝置之驅動方式等而使用介電各向異性不同之各種液晶、及該等之混合物。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. As such a driving method, for example, a twisted nematic (TN, Twisted Nematic) method, a lateral electric field effect display technology (IPS, In-plane Switching) method, an optically compensated birefringence (OCB, Optically Compensated Birefringence) method, and more Domain vertical alignment (MVA, Multi-Domain Vertical Alignment) method, etc. In the present invention, any of these methods can be preferably used. In addition, as the counter substrate, it can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

作為液晶層之形成方法,可使用一般作為液晶單元之製作方法而使用之方法,例如可列舉真空注入方式或液晶滴加方式等。於藉由上述方法而形成液晶層後,藉由將液晶單元緩冷至常溫,可使所封入之液晶配向。 As a method of forming the liquid crystal layer, a method generally used as a method of producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method or a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, by slowly cooling the liquid crystal cell to room temperature, the enclosed liquid crystal can be aligned.

[有機發光顯示裝置] [Organic Light Emitting Display Device]

作為本發明之有機發光顯示裝置,例如可列舉具有上述本發明之彩色濾光器與有機發光體之有機發光顯示裝置。參照圖式對此種本發明之有機發光顯示裝置進行說明。圖3係表示本發明之有機發光顯示裝置之一例之概略圖。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與有機發光體80。亦可於彩色濾光片10與有機發光體80之間具有有機保護層50或無機氧化膜60。 As the organic light-emitting display device of the present invention, for example, an organic light-emitting display device having the above-mentioned color filter and organic light-emitting body of the present invention can be cited. The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of the organic light emitting display device of the present invention. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. It is also possible to have an organic protective layer 50 or an inorganic oxide film 60 between the color filter 10 and the organic light-emitting body 80.

作為有機發光體80之積層方法,例如可列舉:於彩色濾光片上表面逐次形成透明陽極71、電洞注入層72、電洞傳輸 層73、發光層74、電子注入層75及陰極76之方法;或將形成於其他基板上之有機發光體80貼合於無機氧化膜60上之方法等。有機發光體80中之透明陽極71、電洞注入層72、電洞傳輸層73、發光層74、電子注入層75及陰極76,其他構成可適當使用公知者。如此製作之有機發光顯示裝置100例如可應用於被動驅動方式之有機EL顯示器,亦可應用於主動驅動方式之有機EL顯示器。再者,本發明之有機發光顯示裝置並不限定於該圖3所示之構成,可設為一般作為使用彩色濾光片之有機發光顯示裝置所公知之構成。 As a layering method of the organic light-emitting body 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light-emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Method; or a method of attaching an organic light-emitting body 80 formed on another substrate to an inorganic oxide film 60, etc. 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 in the organic light-emitting body 80, and other configurations can be appropriately used known ones. The organic light-emitting display device 100 fabricated in this way can be applied to, for example, an organic EL display in a passive driving mode, and can also be applied to an organic EL display in an active driving mode. Furthermore, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a configuration generally known as an organic light-emitting display device using color filters.

[實施例] [Example]

以下,例示實施例對本發明進行具體說明。本發明並不受該等記載限制。鹽形成前之嵌段共聚合體之酸值,以及藉由上述通式(2)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之酸值係藉由依據JIS K 0070:1992所記載之方法之方法而求出。鹽形成前之嵌段共聚合體之胺值,以及藉由上述通式(2)所表示之化合物進行鹽形成之鹽型嵌段共聚合體之胺值係藉由依據JIS K 7237:1995所記載之方法之方法而求出。鹽形成前及鹽形成後之嵌段共聚合體之羥值係藉由依據JIS K 0070:1992所記載之方法之方法而求出。鹽形成前之嵌段共聚合體之重量平均分子量(Mw)係依照上述本發明之測定方法,藉由GPC(凝膠滲透層析法)作為標準聚苯乙烯換算值而求出。 Hereinafter, the present invention will be explained in detail with examples. The present invention is not limited by these descriptions. The acid value of the block copolymer before salt formation, and the acid value of the salt-type block copolymer formed by the compound represented by the general formula (2) described above are described in accordance with JIS K 0070:1992 Method by method. The amine value of the block copolymer before salt formation, and the amine value of the salt-type block copolymer formed by the compound represented by the above general formula (2) as the salt is based on JIS K 7237: 1995 Method by method. The hydroxyl value of the block copolymer before and after salt formation is obtained by a method based on the method described in JIS K 0070:1992. The weight-average molecular weight (Mw) of the block copolymer before salt formation is determined by GPC (gel permeation chromatography) as a standard polystyrene conversion value in accordance with the above-mentioned measuring method of the present invention.

(實施例1:鹽型嵌段共聚合體A-1之合成) (Example 1: Synthesis of salt type block copolymer A-1)

於具備冷卻管、添加用漏斗、氮氣用入口、機械攪拌機、數位溫度計之500mL圓底四口可分離式燒瓶中添加THF250質量份、 氯化鋰0.6質量份,充分地進行氮氣置換。於將反應燒瓶冷卻至-60℃後,使用注射器注入丁基鋰4.9質量份(15質量%己烷溶液)、二異丙胺1.1質量份、異丁酸甲酯1.0質量份。使用添加用漏斗歷時60分鐘滴加B嵌段用單體之甲基丙烯酸1-乙氧基乙酯(EEMA)2.2質量份、甲基丙烯酸2-乙基己酯(EHMA)12.1質量份、甲基丙烯酸正丁酯(BMA)12.9質量份、甲基丙烯酸苄酯(BzMA)9.0質量份、甲基丙烯酸甲酯(MMA)16.6質量份、甲基丙烯酸2-羥基乙酯(HEMA)17.7質量份。30分鐘後,歷時20分鐘滴加作為A嵌段用單體之甲基丙烯酸二甲胺基乙酯(DMMA)25.3質量份。於反應30分鐘後,添加甲醇1.5質量份而使反應停止。使所獲得之前驅物嵌段共聚合體THF溶液於己烷中再沉澱並進行過濾,藉由真空乾燥進行純化,利用PGMEA進行稀釋,製成固形物成分30質量%溶液。添加32.5質量份之水,升溫至100℃,反應7小時,將源自EEMA之構成單元去保護,製成源自甲基丙烯酸(MAA)之構成單元。使所獲得之嵌段共聚合體A-1" PGMEA溶液於己烷中再沉澱並進行過濾,藉由真空乾燥進行純化。將經純化之嵌段共聚合體A-1"再次溶解於PGMEA400質量份中,添加異氰酸酯A(甲基丙烯酸2-異氰酸基乙酯,商品名:Karenz MOI,昭和電工製造)5.3質量份、二丁基錫(商品名:Neostann U-100,日東化成股份有限公司製造)0.008質量份,升溫至80℃後,反應2小時,獲得具有包含通式(I)所表示之構成單元之A嵌段,以及包含通式(B1)所表示之構成單元與源自含羧基單體之構成單元之B嵌段的嵌段共聚合體A-1'溶液(固形物成分20質量%)。 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed four-neck separable flask equipped with a cooling tube, an addition funnel, an inlet for nitrogen, a mechanical stirrer, and a digital thermometer, and nitrogen substitution was carried out sufficiently. After cooling the reaction flask to -60°C, 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. Using the addition funnel, the monomers for the B block were added dropwise over a period of 60 minutes with 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA), 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), and A 12.9 parts by mass of n-butyl acrylate (BMA), 9.0 parts by mass of benzyl methacrylate (BzMA), 16.6 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA) . After 30 minutes, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for the A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane and filtered, purified by vacuum drying, and diluted with PGMEA to prepare a 30% by mass solution of solid content. 32.5 parts by mass of water was added, the temperature was raised to 100°C, and the reaction was carried out for 7 hours to deprotect the structural unit derived from EEMA to prepare the structural unit derived from methacrylic acid (MAA). The obtained block copolymer A-1" PGMEA solution was reprecipitated in hexane and filtered, and purified by vacuum drying. The purified block copolymer A-1" was re-dissolved in 400 parts by mass of PGMEA , Add isocyanate A (2-isocyanatoethyl methacrylate, trade name: Karenz MOI, manufactured by Showa Denko) 5.3 parts by mass, dibutyltin (trade name: Neostann U-100, manufactured by Nitto Kasei Co., Ltd.) 0.008 Parts by mass, heated to 80°C and reacted for 2 hours to obtain an A block containing the structural unit represented by the general formula (I), and the constituent unit represented by the general formula (B1) and derived from a carboxyl group-containing monomer The B block copolymer A-1' solution (solid content 20% by mass) of the constituent unit.

於100mL圓底燒瓶中加入所獲得之嵌段共聚合體 A-1'溶液50質量份,添加作為上述通式(3)所表示之化合物之苯基膦酸(PPA,東京化成製造)1.27質量份(PPA相對於嵌段共聚合體A-1'之DMMA單元1莫耳為0.5莫耳),於反應溫度30℃下攪拌20小時,藉此獲得固形物成分20質量%之鹽型嵌段共聚合體A-1溶液。鹽形成後之鹽型嵌段共聚合體A-1之酸值與鹽形成前之嵌段共聚合體A-1'相同,鹽形成後之胺值具體而言係以如下方式算出。於NMR試樣管中加入將鹽型嵌段共聚合體A-1(再沉澱後之固形物)9質量份、NMR用氘代氯仿-D191質量份混合而成之溶液1g,使用核磁共振裝置(日本電子製造,FT NMR,JNM-AL400),於室溫、累計次數10000次之條件下測定13C-NMR光譜。所獲得之光譜資料中,根據在末端之氮部位(胺基)中未進行鹽形成之氮原子所鄰接之碳原子峰與進行鹽形成之氮原子所鄰接之碳原子峰之積分值之比率,算出進行鹽形成之胺基數相對於胺基總數之比率,確認到與理論之鹽形成比率相同(所有苯基膦酸與嵌段共聚合體A-1'之DMMA之末端之氮部位形成鹽)。 50 parts by mass of the obtained block copolymer A-1' solution was added to a 100 mL round-bottom flask, and 1.27 parts by mass of phenylphosphonic acid (PPA, manufactured by Tokyo Chemical Industry) as the compound represented by the above general formula (3) was added (PPA is 0.5 mol with respect to 1 mol of DMMA unit of block copolymer A-1'), stirred at a reaction temperature of 30°C for 20 hours, thereby obtaining a salt-type block copolymer with a solid content of 20% by mass A-1 solution. The acid value of the salt-type block copolymer A-1 after the salt formation is the same as the block copolymer A-1′ before the salt formation, and the amine value after the salt formation is specifically calculated as follows. Add 1g of a solution of 9 parts by mass of salt-type block copolymer A-1 (solid after reprecipitation) and 191 parts by mass of deuterated chloroform-D for NMR in the NMR sample tube, and use a nuclear magnetic resonance device ( Made by JEOL, FT NMR, JNM-AL400), 13C-NMR spectrum was measured under the conditions of room temperature and cumulative times of 10,000 times. The obtained spectrum data is calculated based on the ratio of the integral value of the peak of the carbon atom adjacent to the nitrogen atom that does not undergo salt formation at the terminal nitrogen site (amine group) and the peak of the carbon atom adjacent to the nitrogen atom undergoing salt formation The ratio of the number of amine groups for salt formation to the total number of amine groups was confirmed to be the same as the theoretical salt formation ratio (all phenylphosphonic acids form a salt with the nitrogen site at the end of the DMMA of the block copolymer A-1').

(實施例2~14:鹽型嵌段共聚合體A-2~A-14之合成) (Examples 2~14: Synthesis of salt block copolymers A-2~A-14)

於實施例1中,將A嵌段之材料變更為表1所示之含量,將B嵌段之材料變更為表1所示之種類及含量,除此以外,以與實施例1之鹽型嵌段共聚合體A-1相同之方式,獲得鹽型嵌段共聚合體A-2~A-14溶液。再者,甲基丙烯酸1-乙氧基乙酯(EEMA)係使用與表1之MAA相等之莫耳量。又,於表1中,用作鹽形成化合物之有機酸化合物或鹵代烴之量係以相對於通式(I)所表示之構成單元所具有之氮部位(DMMA)1莫耳之上述化合物之莫耳數表示。又,於 實施例2中,將經純化之嵌段共聚合體A-1"再次溶解於PGMEA400質量份中,添加異氰酸酯B(甲基丙烯酸2-(0-[1'-甲基亞丙基胺基]羧基胺基)乙酯,Karenz MOI-BM,昭和電工製造)12.0質量份、二月桂酸二丁基錫0.01質量份,於130℃下加熱2小時,藉此獲得具有包含通式(I)所表示之構成單元之A嵌段、及包含通式(B1)所表示之構成單元與源自含羧基單體之構成單元之B嵌段的嵌段共聚合體A-2'溶液(固形物成分20質量%)。 In Example 1, the A block material was changed to the content shown in Table 1, and the B block material was changed to the type and content shown in Table 1. Otherwise, the same as the salt type of Example 1 In the same way as block copolymer A-1, solutions of salt type block copolymers A-2 to A-14 were obtained. Furthermore, 1-ethoxyethyl methacrylate (EEMA) uses the same molar amount as the MAA in Table 1. In addition, in Table 1, the amount of the organic acid compound or halogenated hydrocarbon used as the salt-forming compound is 1 mol of the above compound relative to the nitrogen site (DMMA) of the structural unit represented by the general formula (I) The number of moles said. In addition, in Example 2, the purified block copolymer A-1" was dissolved again in 400 parts by mass of PGMEA, and isocyanate B (methacrylic acid 2-(0-[1'-methylpropylene amine Carboxylamino) ethyl ester, Karenz MOI-BM, manufactured by Showa Denko) 12.0 parts by mass, 0.01 parts by mass of dibutyltin dilaurate, heated at 130°C for 2 hours, thereby obtaining a compound having the general formula (I) The A block of the structural unit represented by the formula (B1) and the block copolymer A-2' solution of the B block of the structural unit derived from the carboxyl group-containing monomer and the structural unit represented by the general formula (B1) (solid content 20 Mass%).

(比較例1~2:比較鹽型嵌段共聚合體AC-1~AC-2之合成) (Comparative Examples 1~2: Comparison of the synthesis of salt block copolymers AC-1~AC-2)

於實施例1中,將A嵌段之材料變更為表1所示之含量,將B嵌段之材料變更為表1所示之種類及含量,除此以外,以與實施例1之鹽型嵌段共聚合體A-1溶液相同之方式,獲得比較鹽型嵌段共聚合體AC-1~AC-2溶液。再者,於比較例1中,不使經純化之比較嵌段共聚合體AC-1"與異氰酸酯化合物反應,而獲得比較鹽型嵌段共聚合體AC-1溶液。於比較例2中,將丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯與EEMA等B嵌段用單體一起添加,而獲得比較嵌段共聚合體AC-2",不使經純化之比較嵌段共聚合體AC-2"與異氰酸酯化合物反應,而獲得比較鹽型嵌段共聚合體AC-2溶液。 In Example 1, the A block material was changed to the content shown in Table 1, and the B block material was changed to the type and content shown in Table 1. Otherwise, the same as the salt type of Example 1 In the same way as the block copolymer A-1 solution, the comparative salt type block copolymer AC-1~AC-2 solution was obtained. Furthermore, in Comparative Example 1, the purified comparative block copolymer AC-1" was not reacted with an isocyanate compound, and a comparative salt type block copolymer AC-1 solution was obtained. In Comparative Example 2, acrylic acid (3-Ethyloxetane-3-yl) methyl ester is added together with B block monomers such as EEMA to obtain a comparative block copolymer AC-2" without copolymerizing the purified comparative block The composite AC-2" reacted with the isocyanate compound to obtain a comparative salt type block copolymer AC-2 solution.

將實施例1~14中所獲得之鹽型嵌段共聚合體A-1~A-14及比較例1~2中所獲得之比較鹽型嵌段共聚合體AC-1~AC-2中之鹽形成前及鹽形成後之酸值、胺值、羥值、以及鹽形成前之重量平均分子量(Mw)示於表1。再者,鹽型嵌段共聚合體之鹽形成後之胺值係自鹽形成前之胺值減去DMMA單元之胺值而算出。 The salt type block copolymers A-1 to A-14 obtained in Examples 1 to 14 and the comparative salt type block copolymers AC-1 to AC-2 obtained in Comparative Examples 1 to 2 The acid value, amine value, hydroxyl value, and weight average molecular weight (Mw) before salt formation before and after salt formation are shown in Table 1. Furthermore, the amine value of the salt-type block copolymer after salt formation is calculated by subtracting the amine value of the DMMA unit from the amine value before salt formation.

(實施例15:嵌段共聚合體A-15之合成) (Example 15: Synthesis of block copolymer A-15)

於實施例1中,除未進行鹽形成以外,以與實施例1相同之方式獲得嵌段共聚合體A-15溶液。 In Example 1, a block copolymer A-15 solution was obtained in the same manner as in Example 1, except that salt formation was not performed.

(實施例16:嵌段共聚合體A-16之合成) (Example 16: Synthesis of block copolymer A-16)

於實施例3中,除未進行鹽形成以外,以與實施例3相同之方式獲得嵌段共聚合體A-16溶液。 In Example 3, a block copolymer A-16 solution was obtained in the same manner as in Example 3 except that salt formation was not performed.

(實施例17:嵌段共聚合體A-17之合成) (Example 17: Synthesis of block copolymer A-17)

於實施例5中,除未進行鹽形成以外,以與實施例5相同之方式獲得嵌段共聚合體A-17溶液。 In Example 5, a block copolymer A-17 solution was obtained in the same manner as in Example 5 except that salt formation was not performed.

(實施例18:鹽型嵌段共聚合體A-18之合成) (Example 18: Synthesis of salt type block copolymer A-18)

將500ml之四口可分離式燒瓶進行減壓並乾燥後,進行Ar(氬氣)置換。一面進行Ar流動,一面添加脫水THF100質量份、甲基三甲基矽烷基二甲基乙烯酮縮醛2.0質量份、四丁基銨-3-氯苯甲酸酯(TBACB)之1M乙腈溶液0.15ml、均三甲苯0.2質量份。於該處使用滴加漏斗,歷時45分鐘滴加甲基丙烯酸2-乙基己酯(EHMA)12.1質量份、甲基丙烯酸正丁酯(BMA)12.9質量份、甲基丙烯酸苄酯(BzMA)9.0質量份、甲基丙烯酸甲酯(MMA)17.7質量份、甲基丙烯酸2-羥基乙酯(HEMA)17.7質量份。若反應進行則發熱,因此藉由冰浴冷卻而將溫度保持為未滿40℃。1小時後,歷時15分鐘滴加甲基丙烯酸二甲胺基乙酯(DMMA)25.3質量份。反應1 小時後,添加甲醇5質量份使反應停止。將溶劑減壓去除,獲得嵌段共聚合體A-18"。將嵌段共聚合體A-18"溶解於PGMEA400質量份中,添加異氰酸酯A(甲基丙烯酸2-異氰酸基乙酯,商品名:Karenz MOI,昭和電工製造)5.3質量份、二丁基錫(商品名:Neostann U-100,日東化成股份有限公司製造)0.008質量份,升溫至80℃後,反應2小時,獲得具有包含通式(I)所表示之構成單元之A嵌段,以及包含通式(B1)所表示之構成單元與源自含羧基單體之構成單元之B嵌段的嵌段共聚合體A-18'溶液(固形物成分20質量%)。於實施例1中,使用嵌段共聚合體A-18'溶液代替嵌段共聚合體A-1'溶液,除此以外,以與實施例1相同之方式,獲得固形物成分20質量%之鹽型嵌段共聚合體A-18溶液。 After depressurizing and drying a 500ml four-neck separable flask, it was replaced with Ar (argon). While performing Ar flow, add 100 parts by mass of dehydrated THF, 2.0 parts by mass of methyl trimethylsilyl dimethyl ketene acetal, and 1M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) 0.15 ml, 0.2 parts by mass of mesitylene. Using a dropping funnel, 12.1 parts by mass of 2-ethylhexyl methacrylate (EHMA), 12.9 parts by mass of n-butyl methacrylate (BMA), and benzyl methacrylate (BzMA) were added dropwise over 45 minutes. 9.0 parts by mass, 17.7 parts by mass of methyl methacrylate (MMA), and 17.7 parts by mass of 2-hydroxyethyl methacrylate (HEMA). As the reaction progresses, heat is generated, so the temperature was kept below 40°C by cooling in an ice bath. After 1 hour, 25.3 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 15 minutes. After reacting for 1 hour, 5 parts by mass of methanol was added to stop the reaction. The solvent was removed under reduced pressure to obtain block copolymer A-18". The block copolymer A-18" was dissolved in 400 parts by mass of PGMEA, and isocyanate A (2-isocyanatoethyl methacrylate, trade name : Karenz MOI, manufactured by Showa Denko Corporation) 5.3 parts by mass, dibutyltin (trade name: Neostann U-100, manufactured by Nitto Kasei Co., Ltd.) 0.008 parts by mass, heated to 80° C., reacted for 2 hours to obtain a compound having the general formula ( I) the A block of the structural unit represented by the general formula (B1) and the block copolymer A-18' solution (solid form) containing the structural unit represented by the general formula (B1) and the B block of the structural unit derived from the carboxyl group-containing monomer Material composition 20% by mass). In Example 1, the block copolymer A-18' solution was used instead of the block copolymer A-1' solution. Except for this, in the same manner as in Example 1, a salt type with a solid content of 20% by mass was obtained. Block copolymer A-18 solution.

將實施例15~18中所獲得之嵌段共聚合體A-15~A-17及鹽型嵌段共聚合體A-18中之酸值、胺值、羥值及重量平均分子量(Mw)示於表1。 The acid value, amine value, hydroxyl value and weight average molecular weight (Mw) of block copolymers A-15 to A-17 and salt type block copolymers A-18 obtained in Examples 15 to 18 are shown in Table 1.

Figure 107106607-A0101-12-0077-16
Figure 107106607-A0101-12-0077-16

此處,表中各簡稱如以下所述。 Here, the abbreviations in the table are as follows.

DMMA:甲基丙烯酸二甲胺基乙酯 DMMA: Dimethylaminoethyl methacrylate

MAA:甲基丙烯酸 MAA: Methacrylic acid

EHMA:甲基丙烯酸2-乙基己酯 EHMA: 2-ethylhexyl methacrylate

BMA:甲基丙烯酸正丁酯 BMA: n-butyl methacrylate

BzMA:甲基丙烯酸苄酯 BzMA: Benzyl methacrylate

MMA:甲基丙烯酸甲酯 MMA: methyl methacrylate

HEMA:甲基丙烯酸2-羥基乙酯 HEMA: 2-hydroxyethyl methacrylate

HPhPA:丙烯酸2-羥基-3-苯氧基丙酯(商品名:M-600A,共榮社化學股份有限公司製造) HPhPA: 2-hydroxy-3-phenoxypropyl acrylate (trade name: M-600A, manufactured by Kyoeisha Chemical Co., Ltd.)

4HBA:丙烯酸4-羥基丁酯 4HBA: 4-hydroxybutyl acrylate

異氰酸酯A:甲基丙烯酸2-異氰酸基乙酯(商品名:Karenz MOI,昭和電工製造) Isocyanate A: 2-isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko)

異氰酸酯B:甲基丙烯酸2-(0-[1'-甲基亞丙基胺基]羧基胺基)乙酯(商品名:Karenz MOI-BM,昭和電工製造) Isocyanate B: 2-(0-[1'-methylpropyleneamino]carboxyamino)ethyl methacrylate (trade name: Karenz MOI-BM, manufactured by Showa Denko)

異氰酸酯C:異氰酸1,1-(雙丙烯醯氧基甲基)乙酯(商品名:Karenz BEI,昭和電工製造) Isocyanate C: 1,1-(bisacryloxymethyl)ethyl isocyanate (trade name: Karenz BEI, manufactured by Showa Denko)

異氰酸酯D:異氰酸2-甲基丙烯醯氧基乙氧基乙酯(商品名:Karenz MOI-EG,昭和電工製造) Isocyanate D: 2-methacryloxy ethoxy ethyl isocyanate (trade name: Karenz MOI-EG, manufactured by Showa Denko)

異氰酸酯E:丙烯酸2-異氰酸基乙酯(商品名:Karenz AOI-VM,昭和電工製造) Isocyanate E: 2-isocyanatoethyl acrylate (trade name: Karenz AOI-VM, manufactured by Showa Denko)

(合成例1:鹼可溶性樹脂A溶液之合成) (Synthesis example 1: Synthesis of alkali-soluble resin A solution)

於聚合槽中添加PGMEA300質量份,於氮氣環境下升溫至100 ℃後,歷時1.5小時連續地滴加甲基丙烯酸2-苯氧基乙酯(PhEMA)90質量份、MMA54質量份、甲基丙烯酸(MAA)36質量份及Perbutyl O(日油股份有限公司製造)6質量份、鏈轉移劑(正十二烷基硫醇)2質量份。其後,保持100℃繼續進行反應,自上述主鏈形成用混合物之滴加結束起2小時後,添加對甲氧基苯酚0.1質量份作為聚合抑制劑,使聚合終止。其次,一面吹入空氣,一面添加作為含環氧基之化合物之甲基丙烯酸縮水甘油酯(GMA)20質量份,升溫至110℃後,添加三乙胺0.8質量份,於110℃下進行15小時加成反應,獲得鹼可溶性樹脂A溶液(重量平均分子量(Mw)8500,酸值75mgKOH/g,固形物成分40質量%)。再者,上述重量平均分子量之測定方法係將聚苯乙烯作為標準物質,將THF作為洗提液,藉由Shodex GPC System-21H測定重量平均分子量。又,酸值之測定方法係基於JIS K 0070:1992進行測定。 Add 300 parts by mass of PGMEA to the polymerization tank. After the temperature is raised to 100°C in a nitrogen atmosphere, 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, and methacrylic acid are continuously added dropwise over 1.5 hours. (MAA) 36 parts by mass, 6 parts by mass of Perbutyl O (manufactured by NOF Corporation), and 2 parts by mass of chain transfer agent (n-dodecyl mercaptan). Thereafter, the reaction was continued 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 terminate the polymerization. Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy-containing compound was added. After the temperature was raised to 110°C, 0.8 parts by mass of triethylamine was added, and the temperature was carried out at 110°C for 15%. The hourly addition reaction gave an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass). Furthermore, the above-mentioned method for measuring the weight average molecular weight is to measure the weight average molecular weight by Shodex GPC System-21H using polystyrene as the standard substance and THF as the eluent. In addition, the acid value measurement method is based on JIS K 0070:1992.

(實施例21) (Example 21)

(1)色材分散液G1之製造 (1) Manufacturing of color material dispersion G1

將作為分散劑之實施例1之鹽型嵌段共聚合體A-1溶液(固形物成分20質量%)14.8質量份、作為色材之C.I.顏料綠58(PG58)10.4質量份、C.I.顏料黃138(PY138)2.6質量份、合成例1中所獲得之鹼可溶性樹脂A溶液14.6質量份、PGMEA57.6質量份、粒徑2.0mm氧化鋯珠100質量份放入蛋黃醬瓶中,作為預壓碎,藉由塗料振盪機(淺田鐵工股份有限公司製造)振盪1小時,繼而取出粒徑2.0mm氧化鋯珠,添加粒徑0.1mm之氧化鋯珠200質量份,同樣地,作為正式壓碎,於塗料振盪機中進行4小時分散,獲得色材分散液 G1。 14.8 parts by mass of the salt block copolymer A-1 solution (solid content 20% by mass) of Example 1 as a dispersant, 10.4 parts by mass of CI Pigment Green 58 (PG58) as a color material, and CI Pigment Yellow 138 (PY138) 2.6 parts by mass, 14.6 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, 57.6 parts by mass of PGMEA, and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are placed in a mayonnaise bottle as a pre-crush , Shake for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.), then take out the zirconia beads with a particle size of 2.0 mm, add 200 parts by mass of zirconia beads with a particle size of 0.1 mm, and similarly, as a formal crushing, Dispersion was performed in a paint shaker for 4 hours to obtain a color material dispersion G1.

(2)彩色濾光片用感光性著色樹脂組成物G1之製造 (2) Manufacturing of photosensitive colored resin composition G1 for color filters

添加上述(1)中所獲得之色材分散液G1 43.8質量份、合成例1中所獲得之鹼可溶性樹脂A溶液6.3質量份、多官能單體(商品名Aronix M-403,東亞合成股份有限公司製造)5.9質量份、作為光起始劑之肟酯系起始劑(ADEKA公司製造,「Adeka arkls NCI-930」)0.92質量份、肟酯系起始劑(常州強力電子新材料公司製造,「TR-PBG-3057」)0.69質量份、二乙基-9-氧硫

Figure 107106607-A0101-12-0080-66
(日本化藥公司製造,「DETX-S」)0.12質量份、作為抗氧化劑之受阻酚系抗氧化劑(IRGANOX1010,BASF公司製造)0.11質量份、3-甲基丙烯醯氧基丙基三甲氧基矽烷(商品名:KBM503,信越化學工業股份有限公司製造)0.4質量份、Megafac F-559(DIC製造)0.04質量份及作為溶劑之PGMEA 41.4質量份,其後混合至變得均勻為止,獲得彩色濾光片用感光性著色樹脂組成物G1。 Add 43.8 parts by mass of the color material dispersion G1 obtained in (1) above, 6.3 parts by mass of the alkali-soluble resin A solution obtained in Synthesis Example 1, and a multifunctional monomer (trade name Aronix M-403, Toagosei Co., Ltd. Made by the company) 5.9 parts by mass, 0.92 parts by mass of the oxime ester initiator as a photoinitiator (manufactured by ADEKA, "Adeka arkls NCI-930"), and 0.92 parts by mass of the oxime ester initiator (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) , "TR-PBG-3057") 0.69 parts by mass, diethyl-9-oxysulfur
Figure 107106607-A0101-12-0080-66
(Manufactured by Nippon Kayaku Co., Ltd., "DETX-S") 0.12 parts by mass, hindered phenol antioxidant (IRGANOX 1010, manufactured by BASF Corporation) as an antioxidant, 0.11 parts by mass, 3-methacryloxypropyl trimethoxy Silane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 parts by mass, Megafac F-559 (manufactured by DIC) 0.04 parts by mass, and 41.4 parts by mass of PGMEA as a solvent, and then mixed until it becomes uniform to obtain a color Photosensitive colored resin composition G1 for filters.

(3)著色層之形成 (3) Formation of colored layer

使用旋轉塗佈機將上述(2)中所獲得之著色樹脂組成物G1塗佈於厚度0.7mm且100mm×100mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上後,使用加熱板於80℃下乾燥3分鐘,使用超高壓水銀燈照射60mJ/cm2之紫外線,進而於230℃之潔淨烘箱中進行30分鐘後烘烤,藉此以硬化後之膜厚成為2.5μm之方式調整膜厚而形成著色層G1。 Use a spin coater to apply the colored resin composition G1 obtained in (2) above on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm and 100 mm × 100 mm, and then heat it. The board was dried at 80°C for 3 minutes, irradiated with 60mJ/cm 2 of ultraviolet light using an ultra-high pressure mercury lamp, and then post-baked in a clean oven at 230°C for 30 minutes to adjust the cured film thickness to 2.5μm The film is thick and the colored layer G1 is formed.

(實施例22~38、比較例11~12) (Examples 22 to 38, Comparative Examples 11 to 12)

(1)色材分散液G2~G18、比較色材分散液GC1~GC2之製造 (1) Manufacturing of color material dispersion G2~G18 and comparison color material dispersion GC1~GC2

於實施例21之(1)中,代替鹽型嵌段共聚合體A-1溶液,分別如表2所示,以固形物成分成為與鹽型嵌段共聚合體A-1相同之質量份之方式分別使用實施例2~14之鹽型嵌段共聚合體A-2~A-14溶液、實施例15~18之嵌段共聚合體A-15~A-17、鹽型嵌段共聚合體A-18、比較例1~2之比較鹽型嵌段共聚合體AC-1~AC-2溶液,以合計成為100質量份之方式調整PGMEA量,除此以外,以與實施例21之(1)相同之方式,獲得色材分散液G2~G18及比較色材分散液GC1~GC2。 In (1) of Example 21, instead of the salt-type block copolymer A-1 solution, as shown in Table 2, the solid content was the same as that of the salt-type block copolymer A-1. Use the salt type block copolymers A-2~A-14 solutions of Examples 2-14, the block copolymers A-15~A-17 of Examples 15-18, and the salt type block copolymers A-18 respectively. , The comparative salt-type block copolymer AC-1~AC-2 solutions of Comparative Examples 1 and 2, adjust the amount of PGMEA so that the total amount becomes 100 parts by mass. Except for this, the same as in Example 21 (1) In this way, color material dispersion liquids G2 to G18 and comparative color material dispersion liquids GC1 to GC2 are obtained.

(2)彩色濾光片用感光性著色樹脂組成物G2~G18、比較彩色濾光片用感光性著色樹脂組成物GC1~GC2之製造 (2) Manufacture of photosensitive colored resin compositions G2 to G18 for color filters, and photosensitive colored resin compositions GC1 to GC2 for comparative color filters

於實施例21之(2)中,分別使用上述色材分散液G2~G18及上述比較色材分散液GC1~GC2代替色材分散液G1,除此以外,以與實施例21之(2)相同之方式,獲得彩色濾光片用感光性著色樹脂組成物G2~G18、比較彩色濾光片用感光性著色樹脂組成物GC1~GC2。 In (2) of Example 21, the color material dispersions G2 to G18 and the comparative color material dispersions GC1 to GC2 were used instead of the color material dispersion G1. Otherwise, the same as in Example 21 (2) In the same manner, photosensitive colored resin compositions G2 to G18 for color filters and photosensitive colored resin compositions GC1 to GC2 for comparative color filters were obtained.

(3)著色層之形成 (3) Formation of colored layer

於實施例21之(3)中,分別使用上述著色樹脂組成物G2~G18、GC1~GC2代替著色樹脂組成物G1,除此以外,以與實施例21之(3)相同之方式,獲得著色層G2~G18、GC1~GC2。 In (3) of Example 21, the colored resin composition G2 to G18, GC1 to GC2 were used instead of the colored resin composition G1. Except for this, the colored resin composition was obtained in the same manner as in (3) of Example 21. Layers G2~G18, GC1~GC2.

(實施例41) (Example 41)

(1)色材分散液R1之製造 (1) Manufacturing of color material dispersion R1

於實施例21之(1)中,使用下述化學式(R1)所表示之吡咯并吡咯二酮顏料(Irgaphor RED S 3621CF,BASF公司製造)13質量份代替C.I.顏料綠58(PG58)10.4質量份、C.I.顏料黃138(PY138)2.6質量份,除此以外,以與實施例21之(1)相同之方式獲得色材分散液R1。 In (1) of Example 21, 13 parts by mass of diketopyrrolopyrrole pigment (Irgaphor RED S 3621CF, manufactured by BASF) represented by the following chemical formula (R1) was used instead of 10.4 parts by mass of CI Pigment Green 58 (PG58) Except for 2.6 parts by mass of CI Pigment Yellow 138 (PY138), the color material dispersion liquid R1 was obtained in the same manner as in (1) of Example 21.

Figure 107106607-A0101-12-0082-17
Figure 107106607-A0101-12-0082-17

(2)彩色濾光片用感光性著色樹脂組成物R1之製造 (2) Manufacturing of photosensitive colored resin composition R1 for color filters

於實施例21之(2)中,使用上述所獲得之色材分散液R1代替色材分散液G1,除此以外,以與實施例21之(2)相同之方式獲得彩色濾光片用感光性著色樹脂組成物R1。 In (2) of Example 21, the color material dispersion liquid R1 obtained above was used instead of the color material dispersion liquid G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition R1.

(3)著色層之形成 (3) Formation of colored layer

於實施例21之(3)中,使用上述著色樹脂組成物R1代替著色樹脂組成物G1,除此以外,以與實施例21之(3)相同之方式獲得著色層R1。 In Example 21 (3), except that the colored resin composition R1 was used instead of the colored resin composition G1, a colored layer R1 was obtained in the same manner as in Example 21 (3).

(實施例42) (Example 42)

(1)色材分散液B1之製造 (1) Manufacturing of color material dispersion B1

於實施例21之(1)中,使用C.I.顏料藍15:6(PB15:6)13質量份代替C.I.顏料綠58(PG58)10.4質量份、C.I.顏料黃138(PY138)2.6質量份,除此以外,以與實施例21之(1)相同之方式獲得色材分散液B1。 In Example 21 (1), CI Pigment Blue 15:6 (PB15:6) 13 parts by mass was used instead of CI Pigment Green 58 (PG58) 10.4 parts by mass and CI Pigment Yellow 138 (PY138) 2.6 parts by mass, except for this Otherwise, the color material dispersion liquid B1 was obtained in the same manner as in (1) of Example 21.

(2)彩色濾光片用感光性著色樹脂組成物B1之製造 (2) Manufacturing of photosensitive colored resin composition B1 for color filters

於實施例21之(2)中,使用上述所獲得之色材分散液B1代替色材分散液G1,除此以外,以與實施例21之(2)相同之方式獲得彩色濾光片用感光性著色樹脂組成物B1。 In (2) of Example 21, the color material dispersion liquid B1 obtained above was used instead of the color material dispersion liquid G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition B1.

(3)著色層之形成 (3) Formation of colored layer

於實施例21之(3)中,使用上述著色樹脂組成物B1代替著色樹脂組成物G1,除此以外,以與實施例21之(3)相同之方式獲得著色層B1。 In Example 21 (3), except that the colored resin composition B1 was used instead of the colored resin composition G1, a colored layer B1 was obtained in the same manner as in Example 21 (3).

(實施例43) (Example 43)

(1)色材分散液Y1之製造 (1) Manufacturing of color material dispersion Y1

於實施例21之(1)中,使用C.I.分散黃54(商品名:KPPlast Yellow HR,紀和化學製造)13質量份代替C.I.顏料綠58(PG58)10.4質量份、C.I.顏料黃138(PY138)2.6質量份,除此以外,以與實施例21之(1)相同之方式獲得色材分散液Y1。 In Example 21 (1), 13 parts by mass of CI Disperse Yellow 54 (trade name: KPPlast Yellow HR, manufactured by Kiwa Chemical Co., Ltd.) was used instead of 10.4 parts by mass of CI Pigment Green 58 (PG58) and CI Pigment Yellow 138 (PY138) 2.6 Except for the parts by mass, the color material dispersion liquid Y1 was obtained in the same manner as in Example 21 (1).

(2)彩色濾光片用感光性著色樹脂組成物Y1之製造 (2) Manufacturing of photosensitive colored resin composition Y1 for color filters

於實施例21之(2)中,使用上述所獲得之色材分散液Y1代替色材分散液G1,除此以外,以與實施例21之(2)相同之方式獲得彩 色濾光片用感光性著色樹脂組成物Y1。 In (2) of Example 21, the color material dispersion Y1 obtained above was used instead of the color material dispersion G1. Except for this, the photosensitive material for color filter was obtained in the same manner as in Example 21 (2). Colored resin composition Y1.

(3)著色層之形成 (3) Formation of colored layer

於實施例21之(3)中,使用上述著色樹脂組成物Y1代替著色樹脂組成物G1,除此以外,以與實施例21之(3)相同之方式獲得著色層Y1。 In Example 21 (3), except that the colored resin composition Y1 was used instead of the colored resin composition G1, a colored layer Y1 was obtained in the same manner as in Example 21 (3).

[評價方法] [Evaluation method]

<色材分散液之黏度穩定性評價> <Evaluation of Viscosity Stability of Color Material Dispersion>

針對實施例及比較例中所獲得之色材分散液,分別測定剛製備後與於25℃下保存30天後之黏度,由保存前後之黏度算出黏度變化率,評價黏度穩定性。黏度測定係使用振動式黏度計測定25.0±0.5℃下之黏度。將結果示於表2、3。 For the color material dispersions obtained in the Examples and Comparative Examples, the viscosity immediately after preparation and after storage at 25°C for 30 days were measured, and the viscosity change rate was calculated from the viscosity before and after storage to evaluate the viscosity stability. Viscosity is measured by vibrating viscometer at 25.0±0.5℃. The results are shown in Tables 2 and 3.

(黏度穩定性評價基準) (Viscosity stability evaluation standard)

AA:保存前後之黏度之變化率未滿10% AA: The change rate of viscosity before and after storage is less than 10%

A:保存前後之黏度之變化率為10%以上且未滿15% A: The change rate of viscosity before and after storage is more than 10% and less than 15%

B:保存前後之黏度之變化率為15%以上且未滿25% B: The change rate of the viscosity before and after storage is more than 15% and less than 25%

C:保存前後之黏度之變化率為25%以上且未滿40% C: The change rate of viscosity before and after storage is more than 25% and less than 40%

D:保存前後之黏度之變化率為40%以上 D: The change rate of viscosity before and after storage is more than 40%

其中,色材分散液之黏度係相對於包含色材分散液之溶劑在內之合計質量,將色材設為13質量%時之值。即便評價結果為C,色材分散液亦可於實際應用中使用,若評價結果為B,則色材分散液更良好,若評價結果為A,則色材分散液之分散穩定性優異。 Among them, the viscosity of the color material dispersion is the value when the color material is 13% by mass relative to the total mass including the solvent of the color material dispersion. Even if the evaluation result is C, the color material dispersion can be used in practical applications. If the evaluation result is B, the color material dispersion is better, and if the evaluation result is A, the dispersion stability of the color material dispersion is excellent.

<ITO耐龜裂性評價> <ITO crack resistance evaluation>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用感光性著色樹脂組成物以後烘烤後之膜厚成為2.5μm左右之方式分別塗佈於厚度0.7mm且100mm×100mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上。其後,於80℃之加熱板上進行3分鐘加熱乾燥。不介隔光罩地使用超高壓水銀燈照射40mJ/cm2之紫外線,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)。藉由濺鍍裝置(ULVAC製造,CS-200),於所獲得之硬化膜上製膜厚度120nm之ITO。將該膜於25℃之N-甲基吡咯啶酮中浸漬120分鐘後,目視觀察基板是否於ITO膜產生龜裂。 Use a spin coater to apply the photosensitive colored resin composition for color filters obtained in the examples and comparative examples to the thickness of 0.7mm and 100mm×100mm so that the film thickness after baking becomes about 2.5μm. On the glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35"). After that, it was heated and dried on a hot plate at 80°C for 3 minutes. An ultra-high pressure mercury lamp was used to irradiate 40mJ/cm 2 of ultraviolet rays without intervening a light shield, and post-baking was performed in a clean oven at 230°C for 30 minutes to obtain a cured film (colored film). A sputtering device (manufactured by ULVAC, CS-200) was used to form ITO with a thickness of 120 nm on the obtained cured film. After immersing the film in N-methylpyrrolidone at 25°C for 120 minutes, it was visually observed whether the substrate had cracks in the ITO film.

(ITO耐龜裂性評價基準) (Evaluation criteria for ITO crack resistance)

AA:無龜裂產生 AA: no cracks

A:龜裂之產生為5個以下 A: The number of cracks is less than 5

B:整面產生龜裂 B: Cracks on the whole surface

C:整面產生龜裂,ITO局部剝離之狀態 C: The whole surface is cracked and the ITO is partially peeled off

若上述評價基準為AA或A,則可於實際應用中使用,若評價結果為AA,則效果更優異。 If the above evaluation criterion is AA or A, it can be used in practical applications, and if the evaluation result is AA, the effect is more excellent.

<顯影密接性評價> <Evaluation of developing adhesion>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用感光性著色樹脂組成物分別塗佈於厚度0.7mm且100mm×100mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上,其後使用加熱板於80℃下進行3分鐘乾燥,藉此形成厚度2.5μm之著色層。於該著色層介隔具有2~80μm之遮罩開口寬度之光罩 使用超高壓水銀燈照射60mJ/cm2之紫外線。使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液對形成有上述著色層之玻璃板進行60秒噴淋顯影。藉由光學顯微鏡對顯影後之基板進行觀察,觀察相對於遮罩開口線寬之著色層之有無。將結果示於表2、3。 The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm×100 mm using a spin coater. NA35") was then dried using a hot plate at 80°C for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 60mJ/cm 2 in a mask with a mask opening width of 2~80μm between the colored layer. Using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, the glass plate on which the colored layer was formed was shower-developed for 60 seconds. Observe the developed substrate with an optical microscope to observe the presence or absence of the colored layer relative to the line width of the mask opening. The results are shown in Tables 2 and 3.

(顯影密接性評價基準) (Evaluation Criteria for Development Adhesion)

AA:於遮罩開口線寬未滿10μm之部分觀察到著色層 AA: The colored layer is observed in the part where the line width of the mask opening is less than 10μm

A:於遮罩開口線寬10μm以上且未滿20μm之部分觀察到著色層 A: The colored layer is observed in the part where the line width of the mask opening is 10μm or more and less than 20μm

B:於遮罩開口線寬20μm以上且未滿50μm之部分觀察到著色層 B: The colored layer is observed in the part where the line width of the mask opening is 20μm or more and less than 50μm

C:於遮罩開口線寬50μm以上且未滿80μm之部分觀察到著色層 C: The colored layer is observed in the part where the width of the mask opening is 50μm or more and less than 80μm

D:於遮罩開口線寬80μm以下之部分未觀察到著色層 D: No colored layer is observed in the part of the mask opening line width below 80μm

即便評價結果為B,彩色濾光片用感光性著色樹脂組成物亦可於實際應用中使用,若評價結果為A,則彩色濾光片用感光性著色樹脂組成物更適於高精細化,若評價結果為AA,則彩色濾光片用感光性著色樹脂組成物更進一步適於高精細化。 Even if the evaluation result is B, the photosensitive colored resin composition for color filters can be used in practical applications. If the evaluation result is A, the photosensitive colored resin composition for color filters is more suitable for high definition. If the evaluation result is AA, the photosensitive colored resin composition for color filters is more suitable for high definition.

<顯影殘渣評價> <Evaluation of developing residue>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用感光性著色樹脂組成物分別塗佈於厚度0.7mm且100mm×100mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上,其後使用加熱板於60℃下進行3分鐘乾燥,藉此形成厚度2.5μm之著色層。使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液對形成 有上述著色層之玻璃板進行120秒噴淋顯影。於目視觀察上述著色層之形成後之玻璃基板之未曝光部(50mm×50mm)後,利用含有乙醇之鏡頭清潔器(Toray公司製造,商品名Toraysee MK Clean Cloth)充分地擦拭,目視觀察該鏡頭清潔器之著色程度。將結果示於表2、3。 The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm×100 mm using a spin coater. NA35") was then dried using a hot plate at 60°C for 3 minutes, thereby forming a coloring layer with a thickness of 2.5 μm. The glass plate on which the colored layer was formed was shower-developed for 120 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer. After visually observing the unexposed part (50mm×50mm) of the glass substrate after the formation of the colored layer, wipe it thoroughly with an alcohol-containing lens cleaner (manufactured by Toray, trade name Toraysee MK Clean Cloth), and observe the lens visually The degree of coloring of the cleaner. The results are shown in Tables 2 and 3.

(顯影殘渣評價基準) (Evaluation criteria for developing residue)

A:藉由目視未確認到顯影殘渣,鏡頭清潔器完全未著色 A: The developing residue is not confirmed visually, and the lens cleaner is not colored at all

B:藉由目視未確認到顯影殘渣,略微地確認到鏡頭清潔器之著色 B: The development residue was not confirmed visually, and the coloring of the lens cleaner was slightly confirmed

C:藉由目視略微地確認到顯影殘渣,略微地確認到鏡頭清潔器之著色 C: The developing residue is slightly confirmed visually, and the coloring of the lens cleaner is slightly confirmed

D:藉由目視略微地確認到顯影殘渣,確認到鏡頭清潔器之著色 D: The developing residue is slightly confirmed visually, and the coloring of the lens cleaner is confirmed

E:藉由目視確認到顯影殘渣,確認到鏡頭清潔器之著色 E: Visually confirm the development residue and confirm the coloring of the lens cleaner

若顯影殘渣評價基準為A、B或C,則評價為充分地抑制顯影殘渣之產生,可於實際應用中毫無問題地使用。 If the development residue evaluation standard is A, B, or C, it is evaluated that the generation of development residue is sufficiently suppressed, and it can be used in practical applications without any problems.

<溶劑再溶解性評價> <Evaluation of Solvent Resolubility>

使寬度0.5cm、長度10cm之玻璃基板之前端浸漬於實施例及比較例中所獲得之彩色濾光片用感光性著色樹脂組成物中,塗佈於玻璃基板之長度1cm部分。將提拉之玻璃基板以玻璃面變得水平之方式放入恆溫恆濕機中,於溫度23℃、濕度80%RH下,依30分鐘之條件下進行乾燥。其次,使附著有經乾燥之塗膜之玻璃基板於PGMEA中浸漬15秒。此時,目視判別乾燥塗膜之再溶解狀態 並進行評價。將結果示於表2、3。 The front end of a glass substrate with a width of 0.5 cm and a length of 10 cm was immersed in the photosensitive colored resin composition for color filters obtained in the Examples and Comparative Examples, and coated on the 1 cm portion of the glass substrate. Put the lifted glass substrate into a constant temperature and humidity machine such that the glass surface becomes horizontal, and dry it under the conditions of a temperature of 23°C and a humidity of 80%RH for 30 minutes. Next, the glass substrate with the dried coating film attached was immersed in PGMEA for 15 seconds. At this time, the re-dissolution state of the dried coating film was visually judged and evaluated. The results are shown in Tables 2 and 3.

(溶劑再溶解性評價基準) (Evaluation criteria for solvent resolubility)

AA:乾燥塗膜完全溶解 AA: The dried coating film is completely dissolved

A:於溶劑中產生乾燥塗膜之薄片,該薄片不久溶解 A: A flake with a dry coating film is produced in a solvent, and the flake will dissolve soon

B:於溶劑中產生乾燥塗膜之薄片,溶液著色 B: In the solvent to produce dry film flakes, the solution is colored

C:於溶劑中產生乾燥塗膜之薄片,溶液未著色 C: Produce dry film flakes in the solvent, the solution is not colored

D:於溶劑中未產生乾燥塗膜之薄片,溶液未著色 D: No dry film flakes are produced in the solvent, and the solution is not colored

若顯影殘渣評價基準為AA、A或B,則評價為溶劑再溶解性良好,可於實際應用中毫無問題地使用。 If the development residue evaluation standard is AA, A, or B, it is evaluated that the solvent resolubility is good, and it can be used without any problems in practical applications.

<色材昇華性評價> <Evaluation of color material sublimation>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用感光性著色組成物分別塗佈於厚度0.7mm之玻璃基板上,於80℃之加熱板上進行3分鐘加熱乾燥,藉此形成厚度2.5μm之著色層。對該著色層介隔描繪有80μm之線與間隙之條紋圖案之光罩使用超高壓水銀燈照射40mJ/cm2之紫外線。其後,使用0.05質量%氫氧化鉀水溶液作為鹼性顯影液對形成有上述著色層之玻璃板進行60秒噴淋顯影,其後進而利用超純水以60秒洗淨。於所獲得之形成有著色圖案之玻璃基板之0.7mm上表面配置玻璃基板,於230℃之加熱板上加熱30分鐘。藉由目視確認於上表面之玻璃基板有無昇華物,而作為色材之昇華性之評價。 The photosensitive coloring compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate with a thickness of 0.7 mm using a spin coater, and heated and dried on a hot plate at 80°C for 3 minutes. Thereby, a coloring layer with a thickness of 2.5 μm is formed. An ultra-high pressure mercury lamp was used to irradiate ultraviolet rays of 40 mJ/cm 2 on a mask with a stripe pattern of 80 μm lines and gaps drawn on the colored layer. Thereafter, the glass plate on which the colored layer was formed was spray-developed for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with ultrapure water for 60 seconds. A glass substrate was placed on the 0.7 mm upper surface of the obtained glass substrate with the colored pattern formed, and heated on a hot plate at 230°C for 30 minutes. By visually confirming the presence or absence of sublimation on the glass substrate on the upper surface, it was used as an evaluation of the sublimation property of the color material.

(色材昇華性評價基準) (Evaluation criteria for sublimation of color materials)

A:於上表面之玻璃基板不具有由昇華物所產生之著色及析出物 A: The glass substrate on the upper surface does not have the coloring and precipitation produced by the sublimation

B:雖然於上表面之玻璃基板存在由昇華物所產生之著色,但無析出物 B: Although the glass substrate on the upper surface is colored by sublimation, there is no precipitate

C:於上表面之玻璃基板存在由昇華物所產生之著色,亦確認到析出物 C: On the upper surface of the glass substrate, there is coloration caused by sublimation, and precipitates are also confirmed

<基板密接性評價> <Evaluation of Adhesion to Substrate>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用感光性著色樹脂組成物分別塗佈於厚度0.7mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上。其後,於80℃之加熱板上進行3分鐘加熱乾燥後,使用超高壓水銀燈照射60mJ/cm2之紫外線。其後,於230℃之潔淨烘箱中進行30分鐘後烘烤,而獲得膜為2.5μm之著色膜。利用美工刀於所獲得之著色膜切出柵格狀之切縫後,於其上貼附背膠牽條,於垂直方向上快速地剝離。目視觀察著色膜之狀態,基於下述評價基準進行評價。將結果示於表2、3。 The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., "NA35") with a thickness of 0.7 mm using a spin coater . Thereafter, after heating and drying on a hot plate at 80°C for 3 minutes, an ultra-high pressure mercury lamp was used to irradiate ultraviolet rays at 60 mJ/cm 2. Thereafter, post-baking was performed in a clean oven at 230°C for 30 minutes to obtain a colored film with a thickness of 2.5 μm. After cutting out grid-like slits on the obtained colored film with a utility knife, a backing tape is attached to it, and it is quickly peeled off in the vertical direction. The state of the colored film was visually observed and evaluated based on the following evaluation criteria. The results are shown in Tables 2 and 3.

(基板密接性評價基準) (Evaluation criteria for substrate adhesion)

AA:完全未確認到剝離 AA: Peeling is not confirmed at all

A:沿柵格狀之切縫略微地確認到剝離 A: Peeling is slightly confirmed along the grid-shaped slit

B:於由切縫所包圍之部分之內部亦確認到剝離 B: Peeling is also confirmed inside the part surrounded by the slit

若評價結果為AA或A,則對基板之密接性優異,評價為實用範圍。 If the evaluation result is AA or A, the adhesion to the substrate is excellent, and the evaluation is in the practical range.

<光學性能評價> <Optical performance evaluation>

使用旋轉塗佈機將實施例及比較例中所獲得之彩色濾光片用 感光性著色樹脂組成物分別塗佈於厚度0.7mm且100mm×100mm之玻璃基板(NH TECHNO GLASS股份有限公司製造,「NA35」)上,其後使用加熱板於80℃下進行3分鐘乾燥,藉此形成著色層。使用超高壓水銀燈對該著色層照射60mJ/cm2之紫外線。其次,將該著色基板於230℃之潔淨烘箱中進行30分鐘後烘烤,使用Olympus製造之顯微分光測定裝置OSP-SP200測定所獲得之著色基板之色度(x、y)、亮度(Y)。將結果一起示於表2、3。再者,光源使用C光源。 The photosensitive colored resin compositions for color filters obtained in the examples and comparative examples were respectively coated on a glass substrate (manufactured by NH TECHNO GLASS Co., Ltd., NH TECHNO GLASS Co., Ltd.) with a thickness of 0.7 mm and a thickness of 100 mm × 100 mm using a spin coater NA35") was then dried using a hot plate at 80°C for 3 minutes to form a colored layer. An ultra-high pressure mercury lamp was used to irradiate the colored layer with ultraviolet rays of 60 mJ/cm 2. Secondly, the colored substrate was post-baked in a clean oven at 230°C for 30 minutes, and the chromaticity (x, y) and brightness (Y) of the obtained colored substrate were measured using the microscope OSP-SP200 manufactured by Olympus. ). The results are shown in Tables 2 and 3 together. Furthermore, the C light source is used as the light source.

Figure 107106607-A0101-12-0091-18
Figure 107106607-A0101-12-0091-18

Figure 107106607-A0101-12-0092-19
Figure 107106607-A0101-12-0092-19

[結果之彙總] [Summary of Results]

由表2、3之結果可知,關於使用實施例21~38及實施例41~43之彩色濾光片用感光性著色樹脂組成物形成之著色層,其亮度較高,ITO膜之耐龜裂性優異,進而顯影密接性及溶劑再溶解性優異,抑制著色層中之色材之昇華及析出,基板密接性亦優異,上述實施例21~38及實施例41~43之彩色濾光片用感光性著色樹脂組成物係使用如下之嵌段共聚合體作為分散劑,該嵌段共聚合體含有包含上述通式(I)所表示之構成單元之A嵌段,以及包含選自上述通式(B1)所表示之構成單元與上述通式(B2)所表示之構成單元中之至少一種之B嵌段。另一方面,關於使用B嵌段不含選自上述通式(B1)所表示之構成單元及上述通式(B2)所表示之構成單元中之至少一種的鹽型嵌段共聚合體作為分散劑之比較例11及12,其亮度較低,ITO膜之耐龜裂性較差,進而顯影密接性及溶劑再溶解性亦較差,確認到著色層中之色材之昇華或析出。 From the results in Tables 2 and 3, it can be seen that the coloring layer formed by using the photosensitive colored resin composition for color filters of Examples 21 to 38 and Examples 41 to 43 has higher brightness and the ITO film is resistant to cracking Excellent performance, further development adhesion and solvent resolubility, inhibit the sublimation and precipitation of the color material in the colored layer, and excellent substrate adhesion. The above-mentioned Examples 21 to 38 and Examples 41 to 43 are used for color filters The photosensitive colored resin composition uses the following block copolymer as a dispersant, the block copolymer containing the A block containing the structural unit represented by the above general formula (I), and containing selected from the above general formula (B1) B block of at least one of the structural unit represented by) and the structural unit represented by the general formula (B2). On the other hand, regarding the use of a salt-type block copolymer in which the B block does not contain at least one selected from the structural unit represented by the above general formula (B1) and the structural unit represented by the above general formula (B2) as a dispersant In Comparative Examples 11 and 12, the brightness is low, the crack resistance of the ITO film is poor, and the development adhesion and solvent resolubility are also poor. Sublimation or precipitation of the color material in the color layer is confirmed.

Figure 107106607-A0101-11-0003-3
Figure 107106607-A0101-11-0004-4
Figure 107106607-A0101-11-0003-3
Figure 107106607-A0101-11-0004-4

Claims (11)

一種彩色濾光片用色材分散液,其係含有色材、分散劑及溶劑者,且上述分散劑係含有A嵌段與B嵌段之嵌段共聚合體,該A嵌段包含下述通式(I)所表示之構成單元,該B嵌段包含選自下述通式(B1)所表示之構成單元及下述通式(B2)所表示之構成單元中之至少一種,
Figure 107106607-A0101-13-0001-20
(通式(I)中,R 1表示氫原子或甲基,A表示二價連結基,R 2及R 3分別獨立地表示氫原子、或可含有雜原子之烴基,R 2及R 3可相互鍵結而形成環構造)
Figure 107106607-A0101-13-0001-21
(通式(B1)中,A 1表示二價連結基,R 11表示可含有氧原子之二、三或四價之脂肪族烴基或碳原子,R 10及R 12分別獨立地表示氫原子或甲基;n為1、2或3)
Figure 107106607-A0101-13-0002-22
(通式(B2)中,A 2表示二價連結基,A 3及A 4分別獨立地表示二、三或四價之連結基,R 13表示可含有選自氧原子及氮原子中之至少一種之二價烴基,R 14、R 16、R 18及R 19分別獨立地表示可含有氧原子之二價脂肪族烴基,R 10、R 15及R 17分別獨立地表示氫原子或甲基;n 1表示0、1、2或3,n 2表示0或1,n 3表示0、1或2,n 1+n 2為1、2或3,n 1+n 2+n 3為1、2或3;m 1表示1、2或3,m 2表示0、1或2,m 1+m 2為1、2或3)。
A color material dispersion liquid for color filters, which contains a color material, a dispersant, and a solvent, and the dispersant contains a block copolymer of A block and B block, and the A block contains the following general The structural unit represented by the formula (I), the B block contains at least one selected from the structural unit represented by the following general formula (B1) and the structural unit represented by the following general formula (B2),
Figure 107106607-A0101-13-0001-20
(In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R 2 and R 3 can be Mutual bonding to form a ring structure)
Figure 107106607-A0101-13-0001-21
(In the general formula (B1), A 1 represents a divalent linking group, R 11 represents a two-, three- or four-valent aliphatic hydrocarbon group or a carbon atom that may contain an oxygen atom, and R 10 and R 12 each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3)
Figure 107106607-A0101-13-0002-22
(In the general formula (B2), A 2 represents a divalent linking group, A 3 and A 4 each independently represent a divalent, trivalent or tetravalent linking group, and R 13 represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R 14 , R 16 , R 18 and R 19 each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R 10 , R 15 and R 17 each independently represent a hydrogen atom or a methyl group; n 1 represents 0, 1, 2 or 3, n 2 represents 0 or 1, n 3 represents 0, 1 or 2, n 1 + n 2 is 1, 2 or 3, n 1 + n 2 + n 3 is 1, 2 or 3; m 1 represents 1, 2 or 3, m 2 represents 0, 1 or 2, and m 1 + m 2 is 1, 2 or 3).
如請求項1之彩色濾光片用色材分散液,其中,上述分散劑之酸值為1mgKOH/g以上且18mgKOH/g以下。 The color material dispersion liquid for color filters of claim 1, wherein the acid value of the dispersant is 1 mgKOH/g or more and 18 mgKOH/g or less. 如請求項1或2之彩色濾光片用色材分散液,其中,上述分散劑含有由上述通式(I)所表示之構成單元所具有之末端之氮部位之至少一部分、與選自由有機酸化合物及鹵代烴所構成之群中之至少一種形成鹽之鹽型嵌段共聚合體。 The color material dispersion liquid for color filters according to claim 1 or 2, wherein the dispersant contains at least a part of the terminal nitrogen portion of the structural unit represented by the general formula (I), and is selected from organic At least one of the acid compound and the halogenated hydrocarbon forms a salt type block copolymer. 如請求項1或2之彩色濾光片用色材分散液,其中,上述分散 劑之羥值為120mgKOH/g以下。 The color material dispersion liquid for color filters of claim 1 or 2, wherein the hydroxy value of the dispersant is 120 mgKOH/g or less. 如請求項1或2之彩色濾光片用色材分散液,其中,上述色材含有選自由吡咯并吡咯二酮顏料、喹酞酮顏料、酞菁銅顏料、酞菁鋅顏料、喹酞酮染料、香豆素染料、花青染料及該等染料之成鹽化合物所構成之群中之至少一種。 According to claim 1 or 2, the color material dispersion liquid for color filters, wherein the color material contains a diketopyrrolopyrrole pigment, a quinophthalone pigment, a copper phthalocyanine pigment, a zinc phthalocyanine pigment, and a quinophthalone At least one of the group consisting of dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes. 一種分散劑,其係含有A嵌段與B嵌段之嵌段共聚合體,該A嵌段包含下述通式(I)所表示之構成單元,該B嵌段包含選自下述通式(B1)所表示之構成單元及下述通式(B2)所表示之構成單元中之至少一種,
Figure 107106607-A0101-13-0003-23
(通式(I)中,R 1表示氫原子或甲基,A表示二價連結基,R 2及R 3分別獨立地表示氫原子、或可含有雜原子之烴基,R 2及R 3可相互鍵結而形成環構造)
Figure 107106607-A0101-13-0003-24
(通式(B1)中,A 1表示二價連結基,R 11表示可含有氧原子之二、 三或四價之脂肪族烴基或碳原子,R 10及R 12分別獨立地表示氫原子或甲基;n為1、2或3)
Figure 107106607-A0101-13-0004-25
(通式(B2)中,A 2表示二價連結基,A 3及A 4分別獨立地表示二、三或四價之連結基,R 13表示可含有選自氧原子及氮原子中之至少一種之二價烴基,R 14、R 16、R 18及R 19分別獨立地表示可含有氧原子之二價脂肪族烴基,R 10、R 15及R 17分別獨立地表示氫原子或甲基;n 1表示0、1、2或3,n表示0或1,n 3表示0、1或2,n 1+n 2為1、2或3,n 1+n 2+n 3為1、2或3;m 1表示1、2或3,m 2表示0、1或2,m 1+m 2為1、2或3)。
A dispersing agent containing a block copolymer of A block and B block, the A block contains the structural unit represented by the following general formula (I), and the B block contains selected from the following general formula ( At least one of the structural unit represented by B1) and the structural unit represented by the following general formula (B2),
Figure 107106607-A0101-13-0003-23
(In the general formula (I), R 1 represents a hydrogen atom or a methyl group, A represents a divalent linking group, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group that may contain a hetero atom, and R 2 and R 3 can be Mutual bonding to form a ring structure)
Figure 107106607-A0101-13-0003-24
(In the general formula (B1), A 1 represents a divalent linking group, R 11 represents a two-, three-, or four-valent aliphatic hydrocarbon group or carbon atom that may contain an oxygen atom, and R 10 and R 12 each independently represent a hydrogen atom or Methyl; n is 1, 2 or 3)
Figure 107106607-A0101-13-0004-25
(In the general formula (B2), A 2 represents a divalent linking group, A 3 and A 4 each independently represent a divalent, trivalent or tetravalent linking group, and R 13 represents that it may contain at least one selected from the group consisting of oxygen atoms and nitrogen atoms A divalent hydrocarbon group, R 14 , R 16 , R 18 and R 19 each independently represent a divalent aliphatic hydrocarbon group that may contain an oxygen atom, and R 10 , R 15 and R 17 each independently represent a hydrogen atom or a methyl group; n 1 represents 0, 1, 2 or 3, n represents 0 or 1, n 3 represents 0, 1 or 2, n 1 + n 2 is 1, 2 or 3, n 1 + n 2 + n 3 is 1, 2 Or 3; m 1 represents 1, 2 or 3, m 2 represents 0, 1 or 2, and m 1 + m 2 is 1, 2 or 3).
一種彩色濾光片用感光性著色樹脂組成物,其含有請求項1至5中任一項之彩色濾光片用色材分散液、鹼可溶性樹脂、多官能單體及光起始劑。 A photosensitive colored resin composition for a color filter, which contains the color material dispersion liquid for a color filter according to any one of claims 1 to 5, an alkali-soluble resin, a multifunctional monomer, and a photoinitiator. 如請求項7之彩色濾光片用感光性著色樹脂組成物,其中,上述光起始劑含有肟酯。 The photosensitive colored resin composition for color filters according to claim 7, wherein the photoinitiator contains an oxime ester. 如請求項7之彩色濾光片用感光性著色樹脂組成物,其中,上述光起始劑含有至少2種肟酯,且進而含有抗氧化劑。 The photosensitive colored resin composition for color filters according to claim 7, wherein the photoinitiator contains at least two oxime esters and further contains an antioxidant. 一種彩色濾光片,其係至少具備基板及設置於該基板上之著色層者,其特徵在於:該著色層之至少一者為上述請求項7至9中任一項之彩色濾光片用感光性著色樹脂組成物之硬化物。 A color filter comprising at least a substrate and a coloring layer provided on the substrate, characterized in that: at least one of the coloring layers is used for the color filter of any one of claims 7 to 9 above Hardened product of photosensitive colored resin composition. 一種顯示裝置,其具有上述請求項10之彩色濾光片。 A display device having the color filter of claim 10 above.
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