WO2023068201A1 - 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置 - Google Patents

顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置 Download PDF

Info

Publication number
WO2023068201A1
WO2023068201A1 PCT/JP2022/038423 JP2022038423W WO2023068201A1 WO 2023068201 A1 WO2023068201 A1 WO 2023068201A1 JP 2022038423 W JP2022038423 W JP 2022038423W WO 2023068201 A1 WO2023068201 A1 WO 2023068201A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
sulfonic acid
mass
pigment
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/038423
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
宏明 石井
謙一 入木
翔 藤本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP2023554654A priority Critical patent/JPWO2023068201A1/ja
Priority to KR1020247012626A priority patent/KR20240090190A/ko
Priority to CN202280069849.7A priority patent/CN118103464A/zh
Publication of WO2023068201A1 publication Critical patent/WO2023068201A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C09C1/58—Agglomerating, pelleting, or the like by wet methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the present invention relates to a pigment dispersion, a photosensitive resin composition, a cured product, a black matrix (hereinafter sometimes abbreviated as "BM"), and an image display device.
  • BM black matrix
  • a color filter is usually formed by forming a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially forming pixels of three or more different colors such as red, green, and blue in a lattice or stripe pattern. It is formed in a pattern such as a shape or a mosaic shape.
  • the pattern size varies depending on the application of the color filter and each color, but is usually about 5 to 700 ⁇ m.
  • the pigment dispersion method is known as a representative manufacturing method for color filters.
  • a photosensitive resin composition containing a black pigment such as carbon black is applied on a transparent substrate, dried under reduced pressure in a vacuum drying apparatus, and then heated and dried on a hot plate.
  • the BM is formed by curing by high temperature treatment at 200° C. or higher, and this is repeated for each color such as red, green, and blue to form pixels.
  • a color filter with BM and pixels is formed.
  • the drying by heating on the hot plate progresses unevenly, the film thickness uniformity deteriorates, and uneven development may occur on the BM and pixels. There was a problem that was greatly exacerbated.
  • BM is generally arranged between red, green, and blue pixels in a grid, stripe, or mosaic pattern, and has the role of improving contrast by suppressing color mixing between pixels and preventing light leakage. . Therefore, BM is required to have a high light shielding property.
  • BM is required to have a high light shielding property.
  • a step is formed at the overlapping portion due to the influence of the film thickness of the BM. In this overlapping portion, the flatness of the pixels is impaired, and the liquid crystal cell gap becomes nonuniform or the orientation of the liquid crystal is disturbed, resulting in deterioration of the display performance. Therefore, in recent years, there has been a particular demand for thinning and thinning the film thickness of the BM. If unevenness occurs, deterioration in adhesion of the BM becomes particularly noticeable.
  • the pattern line width is 10 ⁇ m or more, even if one side of the BM thin line is inserted by about 1 to 2 ⁇ m (the total of both sides of the thin line is about 2 to 4 ⁇ m), the thin line adhesion to the substrate can be maintained, but the line width is 10 ⁇ m. Since the adhesion area at the BM/substrate interface becomes small in a fine line pattern having a thickness of less than 1 ⁇ m, the degree of reduction in pattern adhesion increases remarkably every time the line width is narrowed by 1 ⁇ m.
  • a photosensitive resin composition that is excellent in fine line adhesion and development solubility, and efforts are being made to improve pigment dispersions that affect fine line properties and development solubility.
  • a dispersing aid in a pigment dispersion, and examples of the dispersing aid include compounds containing a carboxy group, a sulfonic acid group, or a phosphoric acid group. From the viewpoint of industrial applicability, a sulfonic acid group-containing compound may be used.
  • Patent Document 1 development adhesion and residue are improved by blending a dispersion pigment using a dispersing aid (sulfonic acid group-containing compound) having an acid value of 0 to 30 in a specific alkali-soluble resin.
  • a dispersing aid sulfonic acid group-containing compound having an acid value of 0 to 30 in a specific alkali-soluble resin.
  • an object of the present invention is to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
  • the gist of the present invention resides in the following.
  • the (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone.
  • [3] The pigment dispersion according to [1], wherein the (C) sulfonic acid group-containing compound contains a copper phthalocyanine sulfonic acid derivative.
  • the content ratio of the (A) pigment and the (C) sulfonic acid group-containing compound on a mass basis ((A) pigment/(C) sulfonic acid group-containing compound) is 10 or more
  • Any of [1] to [4], wherein the content ratio ((A) pigment/(B) dispersant) on a mass basis of the (A) pigment and the (B) dispersant is 4 or more The pigment dispersion according to 1.
  • Photosensitive containing (A) pigment, (B) dispersant, (C) sulfonic acid group-containing compound, (D) alkali-soluble resin, (E) photopolymerizable compound and (F) photopolymerization initiator
  • the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less
  • the (C) sulfonic acid group-containing compound has an acid value of 40 mgKOH/g or more.
  • a photosensitive resin composition A photosensitive resin composition.
  • the (C) sulfonic acid group-containing compound is a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfone.
  • the photosensitive resin composition according to [7], wherein the (C) sulfonic acid group-containing compound comprises a copper phthalocyanine sulfonic acid derivative.
  • the present invention it is possible to provide a pigment dispersion from which a photosensitive resin composition having excellent solubility and fine line adhesion can be obtained, and a photosensitive resin composition using the same.
  • FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.
  • (meth)acryl means "acryl and/or methacryl", and the same applies to "(meth)acrylate” and "(meth)acryloyl”.
  • total solid content means all components other than the solvent contained in the photosensitive resin composition or the pigment dispersion, even if the components other than the solvent are liquid at room temperature, the solid content include in
  • the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
  • the "amine value” represents the amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. .
  • the measuring method will be described later.
  • the acid value represents an acid value in terms of effective solid content, and is calculated by neutralization titration.
  • the pigment dispersion of the present invention is a pigment dispersion containing (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, wherein the electrical conductivity of the (C) sulfonic acid group-containing compound is 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
  • a photosensitive resin composition is prepared using the pigment dispersion of the present invention, the solubility and fine line adhesion are excellent.
  • a photosensitive resin composition can be obtained.
  • the pigment dispersion of the present invention may further contain other components as necessary, such as solvents, alkali-soluble resins, and dyes.
  • solvents such as solvents, alkali-soluble resins, and dyes.
  • the solvent and alkali-soluble resin used in the photosensitive resin composition of the present invention, which will be described later, can be preferably used.
  • the pigment dispersion of the present invention contains (A) a pigment.
  • (A) Pigment refers to a pigment that colors the pigment dispersion and the photosensitive resin composition of the present invention.
  • pigments of various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used.
  • organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments
  • various inorganic pigments can also be used. is.
  • pigments that can be used in the present invention are shown below by pigment numbers.
  • terms such as "C.I. Pigment Red 2" mentioned below mean a color index (C.I.).
  • red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168,
  • C.I. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 more preferably C.I. I. Pigment Blue 15:6,60 may be mentioned.
  • C.I. I. Pigment Green 1 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59 .
  • C.I. I. Pigment Green 7, 36, 58, 59 can be mentioned.
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180, 185 can be mentioned.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
  • C.I. I. Pigment Orange 38, 64, 71 may be mentioned.
  • C.I. I. Pigment Violet 1 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
  • C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 may be mentioned.
  • a black pigment can be used as the pigment (A).
  • the black pigment may be a black pigment alone or a mixture of red, green, blue, and the like.
  • these pigments can be appropriately selected from inorganic or organic pigments.
  • Pigments that can be mixed to prepare black pigments include, for example, Victoria Pure Blue (42595), Auramine O (41000), Catilone Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). , Safranin OK 70:100 (50240), Erioglaucine X (42080), No.
  • 120/Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), First Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15:6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36) (Note that the numbers in ( ) above mean the color index (C.I.).).
  • C.I. I. When indicated by number, for example, C.I. I. yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. I. red pigment 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I. violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. blue pigment 15, 15:1, 15:4, 22, 60, 64, C.I. I. green pigment 7, C.I. I. Brown pigments 23, 25, 26 may be mentioned.
  • black pigments examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
  • black pigments when a black pigment is used, the above-described black pigment that can be used alone is preferable from the viewpoint of light shielding rate and image characteristics, and carbon black is particularly preferable.
  • carbon black examples include the following carbon blacks.
  • pigments for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can be used. These various pigments can also be used in combination of multiple types. For example, a green pigment and a yellow pigment can be used together, or a blue pigment and a violet pigment can be used together for chromaticity adjustment.
  • the average particle size of the pigment (A) used in the present invention is not particularly limited as long as it can develop a desired color when used as a black matrix for a color filter, for example, and is also dependent on the type of pigment used. Although different, it is preferably 10 to 100 nm, more preferably 10 to 70 nm. When the average particle diameter of the pigment is within the above range, the color characteristics of the liquid crystal display device manufactured using the pigment dispersion of the present invention tend to be of high quality.
  • the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and preferably 20 nm or more. For example, 20 to 60 nm is preferable, and 20 to 50 nm is more preferable.
  • the average particle size of the pigment can be obtained by directly measuring the size of primary particles from an electron micrograph. Specifically, the short axis diameter and long axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle.
  • the volume (mass) of each particle is obtained by approximating the rectangular parallelepiped of the obtained particle diameter, and the volume average particle diameter is obtained and taken as the average particle diameter.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the pigment dispersion of the present invention may also contain a dye as long as the effect of the present invention is not affected.
  • Dyes that can be used in combination include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes examples include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 is mentioned.
  • anthraquinone dyes examples include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 may be mentioned.
  • C.I. I. Vat Blue 5 can be used as a quinoneimine dye, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 can be used as a quinoline dye, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 can be used as a nitro dye, for example C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 is mentioned.
  • the photosensitive resin composition using the pigment dispersion of the present invention can be used for various applications described later, but the excellent image formability is particularly high when it is used to form a black matrix for color filters. Effective.
  • a black pigment such as the carbon black or titanium black described above may be used, or a plurality of types of pigments other than black may be mixed and adjusted to black. .
  • the photosensitive resin composition of the present invention which will be described later, has a large effect on fine line adhesion in a region where the pigment concentration is high. Especially in recent years, it is necessary to increase the pigment concentration in order to increase the degree of light blocking.
  • the content of the pigment (A) in such a region where the effect is increased is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total solid content of the photosensitive resin composition. , 52% by mass or more is particularly preferred. From the viewpoint of image forming performance, it is preferably 70% by mass or less, more preferably 65% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 30 to 70% by mass is preferable, 40 to 70% by mass is more preferable, 50 to 65% by mass is even more preferable, and 52 to 65% by mass is particularly preferable.
  • a photosensitive resin composition with high light-shielding properties can be obtained by setting the pigment content within the above range. Specifically, by setting the content of the pigment (A) to 50% by mass or more relative to the total solid content of the photosensitive resin composition, a black matrix having a thickness of 1 ⁇ m is formed using the photosensitive resin composition of the present invention.
  • the optical density when formed can be set to a value of 4.0 or more. The optical density is more preferably 4.1 or higher, still more preferably 4.2 or higher. In areas with high light-shielding properties, peeling of the patterning due to development is likely to be observed. The thin wire adhesion effect of the present invention can be well confirmed.
  • the content of (A) pigment is not particularly limited, but (D) per 100 parts by mass of alkali-soluble resin, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, More preferably 100 parts by mass or more, still more preferably 120 parts by mass or more, even more preferably 150 parts by mass or more, particularly preferably 180 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass parts or less, more preferably 250 parts by mass or less.
  • (A) When the content of the pigment is equal to or higher than the lower limit, it tends to suppress the deterioration of the solubility of the unexposed area in the developing solution. tend to improve.
  • the above upper and lower limits can be combined arbitrarily. For example, preferably 20 to 500 parts by mass, more preferably 50 to 500 parts by mass, still more preferably 100 to 300 parts by mass, even more preferably 120 to 300 parts by mass, even more preferably 150 to 250 parts by mass, particularly preferably is 180 to 250 parts by mass.
  • the pigment dispersion liquid of the present invention contains (B) a dispersant because it is important to finely disperse (A) the pigment and stabilize the dispersion state in order to ensure the stability of the quality.
  • a dispersant a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxy group; Polymeric dispersants having functional groups such as primary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred.
  • polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred.
  • basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are particularly preferred.
  • polymer dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
  • examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants include trade names of EFKA (registered trademark, manufactured by EFKA Chemicals B.V. (EFKA)), Disperbyk (registered trademark, manufactured by BYK-Chemie), and Disparon (registered trademark).
  • EFKA registered trademark, manufactured by EFKA Chemicals B.V.
  • Disperbyk registered trademark, manufactured by BYK-Chemie
  • Disparon registered trademark
  • Kusumoto Kasei Co., Ltd. SOLSPERSE (registered trademark, manufactured by Lubrizol)
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow or Floren registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.
  • Ajisper registered trademark, Ajinomoto Fine manufactured by Techno Co., Ltd.
  • One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.
  • urethane polymer dispersant and/or an acrylic polymer dispersant having a basic functional group as the (B) dispersant in terms of fine line adhesion and linearity.
  • urethane-based polymer dispersants are preferred from the standpoint of fine wire adhesion.
  • Polymeric dispersants having basic functional groups and polyester and/or polyether bonds are preferred from the standpoint of dispersibility and storage stability.
  • the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less.
  • Mw weight average molecular weight
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably from 700 to 100,000, more preferably from 700 to 50,000, even more preferably from 1,000 to 30,000.
  • urethane-based and acrylic polymer dispersants include Disperbyk 160-167, 182 series (all of which are urethane-based), Disperbyk 2000, 2001, etc.
  • Disperbyk 167 and 182 are particularly preferred urethane polymer dispersants having a polyester and/or polyether bond and having a weight average molecular weight of 30,000 or less.
  • Urethane polymer dispersants include, for example, polyisocyanate compounds, compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and compounds having active hydrogen and a tertiary amino group in the same molecule. and a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting with.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
  • Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type, and may use 2 or more types together.
  • trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part
  • trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
  • Examples of compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Those alkoxylated with 25 alkyl groups and mixtures of two or more thereof are included.
  • Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof.
  • polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of
  • Polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly( polyoxytetramethylene)adipate.
  • the most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentane
  • polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate
  • polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned. These may be used individually by 1 type, and may use 2 or more types together.
  • the compound having one or two hydroxyl groups in the same molecule preferably has a number average molecular weight of 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom
  • active hydrogen includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group.
  • a hydrogen atom of the amino group of is preferred.
  • the tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
  • Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, 4-butanediamine may be mentioned.
  • the nitrogen-containing heterocyclic ring includes, for example, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, and benzimidazole ring.
  • N-containing hetero five-membered rings such as benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring
  • nitrogen-containing heterocycles are imidazole rings and triazole rings.
  • Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole.
  • Examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4 -triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl -1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole.
  • N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable. These may be used individually by 1 type, and may use 2 or more types together.
  • the compounding ratio of raw materials when producing a urethane polymer dispersant is 100 parts by mass of a polyisocyanate compound, and a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule, preferably 10. ⁇ 200 parts by mass, more preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, a compound having active hydrogen and a tertiary amino group in the same molecule, preferably 0.2 to 25 parts by mass, more It is preferably 0.3 to 24 parts by mass.
  • Urethane-based polymer dispersants are produced according to known methods for producing polyurethane resins.
  • Solvents for production include, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane.
  • Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.
  • a urethanization reaction catalyst may be used in the above production.
  • this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; triethylamine and triethylenediamine; and a tertiary amine-based catalyst. These may be used individually by 1 type, and may use 2 or more types together.
  • the amine value of the dispersant is expressed by the mass of KOH equivalent to the amount of base per 1 g of the solid content excluding the solvent in the dispersant sample, and can be measured by the following method. Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO 4 (perchloric acid) acetic acid solution.
  • the inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.
  • Amine value [mgKOH/g] (561 x V)/(W x S) [However, W: Amount of weighed dispersant sample [g], V: Amount of titration [mL] at the end point of titration, S: Solid content concentration [% by mass] of dispersant sample. ]
  • the introduction amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled to 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably 5 to 95 mgKOH/g.
  • the amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the amine value is above the lower limit, the dispersibility tends to be good, and when the amine value is below the upper limit, the developability tends to be good.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 30,000 or less. For example, 1,000 to 30,000 is preferred, 2,000 to 30,000 is more preferred, and 3,000 to 30,000 is even more preferred.
  • the dispersibility and dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility tends to be improved by setting the amount to the upper limit or less.
  • the molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is particularly high.
  • Such particularly preferred commercially available urethane dispersants include, for example, Disperbyk 167 and 182 (manufactured by BYK-Chemie).
  • the content ratio ((A) pigment/(B) dispersant) based on mass of (A) pigment and (B) dispersant is preferably 1 or more, more preferably 3 or more, and 4 More preferably, 5 or more is particularly preferable. Moreover, it is preferably 50 or less, more preferably 30 or less, and particularly preferably 15 or less.
  • the content is at least the above lower limit, the development solubility tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 50 are preferred, 3 to 50 are more preferred, 4 to 30 are even more preferred, and 5 to 15 are particularly preferred.
  • the content of the dispersant (B) described later in the photosensitive resin composition of the present invention is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 50% by mass or less, more preferably 30% by mass. % or less, more preferably 20% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass % or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 30% by mass, still more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass.
  • the content ratio of the dispersant (B) described later in the photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the (A) pigment. More preferably 15 parts by mass or more, preferably 200 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 50 parts by mass or less.
  • the lower limit By making it equal to or higher than the lower limit, there is a tendency to easily ensure sufficient dispersibility.
  • the content to the above upper limit or less, there is a tendency to easily achieve sufficient color density, sensitivity, film formability, etc., without reducing the ratio of other components.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 200 parts by mass, more preferably 10 to 80 parts by mass, still more preferably 15 to 50 parts by mass.
  • the pigment dispersion liquid of the present invention contains (C) a sulfonic acid group-containing compound in order to improve dispersibility and storage stability.
  • the (C) sulfonic acid group-containing compound include azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, quinophthalone compounds, isoindolinone compounds, dioxazine compounds, anthraquinone compounds, indanthrene compounds, perylene compounds, and perinone compounds. derivatives of diketopyrrolopyrrole-based and dioxazine-based compounds. Among them, derivatives of phthalocyanine-based and quinophthalone-based compounds are preferred.
  • the sulfonic acid group-containing compound has a sulfonic acid group, and other substituents include, for example, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. Examples thereof include compounds that may be bonded directly to the skeleton of the compound or via, for example, an alkyl group, an aryl group, or a heterocyclic group.
  • the sulfonic acid group-containing compound has, in addition to the sulfonic acid group, other substituents such as a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group. These other substituents may be plurally substituted on the skeleton of one compound.
  • substituents such as a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. directly or via, for example, an alkyl group, an aryl group, or a heterocyclic group.
  • Sulfonic acid group-containing compounds include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. More preferably a phthalocyanine sulfonic acid derivative, and even more preferably a copper phthalocyanine sulfonic acid derivative.
  • the (C) sulfonic acid group-containing compound includes a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, or a dioxazine sulfonic acid derivative.
  • Acid derivatives are preferred, phthalocyanine sulfonic acid derivatives are more preferred, and copper phthalocyanine sulfonic acid derivatives are even more preferred. These may be used individually by 1 type, and may use 2 or more types together.
  • the content of (C) the sulfonic acid group-containing compound contained in the pigment dispersion of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the pigment dispersion. It is more preferably 1.0% by mass or more, more preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5.0% by mass or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved. Further, when the content is equal to or less than the above upper limit, there is a tendency that the pigment aggregation is suppressed and the coated film surface becomes uniform.
  • the content ratio ((A) pigment/(C) sulfonic acid group-containing compound) of (A) pigment and (C) sulfonic acid group-containing compound on a mass basis is preferably 10 or more. 20 or more is more preferable, and 25 or more is particularly preferable. Also, it is preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, and particularly preferably 50 or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the adhesion to the substrate is improved.
  • dispersion stability to improve by making it below the said upper limit.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 are preferred, 10 to 150 are more preferred, 20 to 100 are even more preferred, and 25 to 50 are particularly preferred.
  • the content ratio of (C) the sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more relative to the total solid content of the photosensitive resin composition. , 0.5% by mass or more is more preferable, 1.0% by mass or more is more preferable, and 10% by mass or less is preferable, and 5% by mass or less is more preferable.
  • the content is at least the above lower limit, there is a tendency that the development solubility is improved. Further, when the content is set to the upper limit value or less, the developability tends to be stable and the patterning adhesion tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1.0 to 5% by mass is even more preferable.
  • the electrical conductivity of the sulfonic acid group-containing compound is 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less.
  • the electrical conductivity of the (C) sulfonic acid group-containing compound is expressed by the electrical conductivity when the (C) sulfonic acid group-containing compound is stirred in ultrapure water so as to form a 5% solution, and is measured with an electrical conductivity meter. be able to.
  • the unit can be described in ⁇ S/cm.
  • the electrical conductivity of the sulfonic acid group-containing compound is 2000 ⁇ S/cm or more, preferably 2500 ⁇ S/cm or more, more preferably 3000 ⁇ S/cm or more, and 9000 ⁇ S/cm or less, preferably 8000 ⁇ S/cm or less. , 7000 ⁇ S/cm or less.
  • the content is equal to or higher than the lower limit, there is a tendency that the dispersion stability is improved.
  • the content is equal to or less than the above upper limit, there is a tendency that undercut is suppressed and development adhesion is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is 2000 to 9000 ⁇ S/cm, preferably 2500 to 8000 ⁇ S/cm, more preferably 3000 to 7000 ⁇ S/cm.
  • the acid value of the sulfonic acid group-containing compound is 40 mgKOH/g or more, preferably 60 mgKOH/g or more, more preferably 80 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more; Also, it is preferably 500 mgKOH/g or less, more preferably 300 mgKOH/g or less, still more preferably 200 mgKOH/g or less, and particularly preferably 150 mgKOH/g or less.
  • the solubility tends to be improved by adjusting the content to be equal to or higher than the above lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that undercutting is suppressed and fine line adhesion is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 40 to 500 mgKOH/g is preferred, 60 to 500 mgKOH/g is more preferred, 80 to 300 mgKOH/g is still more preferred, 90 to 200 mgKOH/g is even more preferred, and 100 to 150 mgKOH/g is particularly preferred.
  • the pigment dispersion of the present invention for example, (A) a pigment, (B) a dispersant and (C) a sulfonic acid group-containing compound, and optionally various materials used are dissolved or dispersed in a solvent.
  • a solvent water or an organic solvent used in the photosensitive resin composition of the present invention, which will be described later, can be suitably used.
  • the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the pigment dispersion is preferably 5% by mass or more. , More preferably 10% by mass or more, still more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less be.
  • the content is at least the lower limit, the coloring power is improved, and the optical density (OD value) tends to be easily increased.
  • the amount is equal to or less than the above upper limit, there is a tendency that the dispersion stability becomes good.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, even more preferably 10 to 40% by mass, particularly preferably 20 to 35% by mass.
  • the photosensitive resin composition of the present invention includes (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator.
  • the (C) sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less, and the acid value of the (C) sulfonic acid group-containing compound is 40 mgKOH/g or more.
  • the (A) pigment, (B) dispersant, and (C) sulfonic acid group-containing compound contained in the photosensitive resin composition of the present invention can be preferably used.
  • Alkali-soluble resin especially if the solubility of the exposed area and the non-exposed area in alkali development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed.
  • the alkali-soluble resin is preferably an alkali-soluble resin having a carboxy group.
  • those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxyl group are more preferable. An example is shown below.
  • the (D) alkali-soluble resin in the present invention preferably contains an alkali-soluble resin (d1) having a partial structure represented by the following general formula (d1-1). Including the alkali-soluble resin (d1) tends to improve adhesion.
  • the benzene ring in formula (d1-1) may be further substituted with any substituent.
  • Each R7 independently represents a hydrogen atom or a methyl group.
  • Each X independently represents O, S, CO, or a direct bond.
  • Each * represents a bond.
  • n represents an integer of 0 to 4;
  • n is preferably 3 or less, more preferably 2 or less, and even more preferably 0 from the viewpoint of sensitivity.
  • R7 is preferably a hydrogen atom.
  • X is preferably a direct bond from the viewpoint of sensitivity.
  • Alkali-soluble resin (d1) having a partial structure represented by formula (d1-1) is obtained, for example, by adding (meth)acrylic acid to an epoxy resin having a cardo skeleton represented by formula (d7-1) below. Furthermore, it is preferably an alkali-soluble resin obtained by reacting a polybasic acid and/or its anhydride.
  • the benzene ring in formula (d7-1) may be further substituted with any substituent.
  • Each X independently represents O, S, CO, or a direct bond.
  • n represents an integer of 0 to 4;
  • n represents an integer of 0 to 4, preferably 3 or less, more preferably 2 or less, and even more preferably 0.
  • a known technique can be used as a method for adding (meth)acrylic acid to the epoxy resin.
  • the reaction can be carried out at a temperature of 50-150° C. in the presence of an esterification catalyst.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
  • the amount of (meth)acrylic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the epoxy resin.
  • polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexacarboxylic acid, One or more selected from hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof can be mentioned.
  • polybasic acid and/or its anhydride For the addition reaction of polybasic acid and/or its anhydride, a known method can be used, and the desired product can be obtained by continuous reaction under the same conditions as the addition reaction of (meth)acrylic acid. .
  • Polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol are added during the addition reaction synthesis of the alkali-soluble resin (d1) polybasic acid and/or its anhydride to introduce a multibranched structure. good.
  • Alkali-soluble resin (d1) for example, after mixing a reaction product of epoxy resin and (meth)acrylic acid with polybasic acid and / or its anhydride, or after mixing epoxy resin and (meth)acrylic acid It is obtained by heating after mixing a polybasic acid and/or its anhydride and a polyhydric alcohol with a reactant.
  • the order of mixing the polybasic acid and/or its anhydride and the polyhydric alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride undergo an addition reaction with any hydroxyl group present in the mixture of the reaction product with (meth)acrylic acid and the polyhydric alcohol.
  • the amount of the polyhydric alcohol used is the amount of the reaction product of the epoxy resin and (meth)acrylic acid and the polybasic acid and / or its anhydride from the viewpoint of exhibiting the effect while suppressing thickening and gelation. It is usually about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight, the reactant.
  • the alkali-soluble resin (d1) may be used alone, or two or more resins may be mixed and used.
  • the acid value of the alkali-soluble resin (d1) is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, still more preferably 80 mgKOH/g or more, particularly preferably 80 mgKOH/g or more, and 200 mgKOH/g or less. is preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less. Residue tends to be reduced by making it equal to or higher than the lower limit. Moreover, there is a tendency that fine wire adhesion can be improved by adjusting the content to be equal to or less than the above upper limit. The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, 80 to 150 mgKOH/g is even more preferred, and 80 to 120 mgKOH/g is particularly preferred.
  • the polystyrene equivalent weight average molecular weight (Mw) of the alkali-soluble resin (d1) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 2000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. . Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 7,000 or less. By making it more than the said lower limit, there exists a tendency for thin line
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 2,000 to 10,000 is even more preferred, 4,000 to 8,000 is even more preferred, and 5,000 to 7,000 is particularly preferred.
  • the photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the alkali-soluble resin (d1) as the (D) alkali-soluble resin.
  • the alkali-soluble resin other than the alkali-soluble resin (d1) after the coating film obtained by applying and drying the photosensitive resin composition is exposed, the solubility of the exposed area and the non-exposed area in alkali development changes.
  • it is not particularly limited as long as it is a substance, it is preferably an alkali-soluble resin having a carboxy group.
  • those having an ethylenically unsaturated group are preferable, and alkali-soluble resins having an ethylenically unsaturated group and a carboxy group are more preferable.
  • Specific examples include an epoxy (meth)acrylate resin (d2) having a carboxy group other than the alkali-soluble resin (d1), an acrylic copolymer resin (d3), and other resins (d4).
  • Epoxy (meth)acrylate resin (d2) having a carboxy group other than alkali-soluble resin (d1) for example, the following epoxy (meth)acrylate resin (d2-1), epoxy (meth)acrylate resin (d2-2 ).
  • ⁇ Epoxy (meth)acrylate resin (d2-2)> An ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and/or its anhydride. Alkali-soluble resin obtained by
  • epoxy resins used as raw materials include bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corp.'s "jER (registered trademark; the same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.), bisphenol Epoxy obtained by reaction of alcoholic hydroxyl group of A-type epoxy resin and epichlorohydrin (for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • bisphenol A type epoxy resins e.g., Mitsubishi Chemical Corp.'s "jER (registered trademark; the same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.
  • bisphenol Epoxy obtained by reaction of alcoholic hydroxyl group of A-type epoxy resin and epichlorohydrin for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • TEPIC trisphenolmethane type epoxy resin
  • EPPN registered trademark
  • EPPN-502 manufactured by Nippon Kayaku Co., Ltd.
  • EPPN-503 trisphenolmethane type epoxy resin
  • alicyclic epoxy resins (“Celoxide (registered trademark) 2021P” and “Celoxide EHPE” manufactured by Daicel)
  • glycidylated phenolic resins by the reaction of dicyclopentadiene and phenol.
  • Epoxy resins e.g., "EXA-7200” manufactured by DIC Corporation, "NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • epoxy resins represented by the following general formulas (d2-a) to (d2-e) are preferred.
  • b11 indicates an average value and indicates a number from 0 to 10.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.
  • a plurality of R 11 present in one molecule may be the same or different.
  • b12 represents an average value and represents a number from 0 to 10.
  • R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 21 in one molecule may be the same or different.
  • X represents a linking group represented by general formula (d2-c-1) or (d2-c-2) below. However, it contains one or more adamantane structures in its molecular structure.
  • b13 represents an integer of 2 or 3;
  • R 31 to R 34 and R 35 to R 37 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group.
  • the * mark in the formula represents the binding site in (d2-c).
  • each of R 51 to R 54 is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • each R 55 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; It is an alkylene group.
  • k is an integer of 1 to 5
  • l is an integer of 0 to 13
  • m is each independently an integer of 0 to 5.
  • n and o are each independently an integer of 1-9.
  • R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group.
  • a plurality of R 23 present in one molecule may be the same or different.
  • Examples of ⁇ , ⁇ -unsaturated monocarboxylic acids or ⁇ , ⁇ -unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 - (meth) acryloyloxyethyl phthalate, 2-(meth) acryloyloxyethyl hexahydrophthalate, 2-(meth) acryloyloxyethyl maleate, 2-(meth) acryloyloxypropyl succinate, 2 - (meth) acryloyloxy
  • a monomer or Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth)acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri(meth)acrylate, (anhydrous) succinic acid examples include (meth)acrylic esters to which an acid (anhydride) such as (anhydride) phthalic acid and (anhydride) maleic acid is added and which has one or more ethylenically unsaturated groups and one carboxyl group at the end. (Meth)acrylic acid dimers are also included.
  • (meth)acrylic acid is particularly preferable from the viewpoint of sensitivity.
  • a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to an epoxy resin a known technique can be used.
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150° C. in the presence of an esterification catalyst. can.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , dodecyltrimethylammonium chloride and the like can be used.
  • tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine
  • tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and
  • the epoxy resin, the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used singly, or two kinds may be used. You may use the above together.
  • the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents per equivalent of the epoxy group of the epoxy resin. , 0.7 to 1.1 equivalents is more preferred.
  • the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group By setting the amount of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to the above lower limit or more, the amount of the unsaturated group introduced becomes sufficient, and the subsequent polybasic acid And/or the reaction with its anhydride becomes sufficient, and there is a tendency that a large amount of epoxy groups can be suppressed from remaining.
  • the amount to be equal to or less than the upper limit it is possible to suppress the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group from remaining as an unreacted product.
  • the same compound as the alkali-soluble resin (d1) can be used as the polybasic acid and/or its anhydride and polyhydric alcohol. Also, the same synthetic method as that for the alkali-soluble resin (d1) can be used.
  • the acid value of the epoxy (meth)acrylate resins (d2-1, d2-2) thus obtained is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 50 to 200 mgKOH/g is more preferred, and 80 to 150 mgKOH/g is even more preferred.
  • the polystyrene equivalent weight average molecular weight (Mw) of the epoxy (meth)acrylate resins (d2-1, d2-2) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, and 2000 or more. is more preferable, and 2300 or more is particularly preferable. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. When the content is at least the above lower limit, sensitivity, coating film strength and alkali resistance tend to be improved.
  • the developability and the re-solubility can be improved by adjusting the content to the above upper limit or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,000 to 15,000 is more preferred, 1,500 to 10,000 is even more preferred, 2,000 to 8,000 is even more preferred, and 2,300 to 6,000 is particularly preferred.
  • acrylic copolymer resin (d3) examples include Japanese Patent Laid-Open Nos. 7-207211, 8-259876, 10-300922, and 11-140144. Publications, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Publication No. 2000-56118, Japanese Patent Application Publication No. 2003-233179, Japanese Patent Application Publication No. 2007-270147, etc. Any polymeric compound can be used. Preferred are the following acrylic copolymer resins (d3-1) to (d3-4). Among them, the acrylic copolymer resin (d3-1) is particularly preferred.
  • Acrylic copolymer resin (d3-1) for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least some of the epoxy groups of the copolymer are unsaturated A resin obtained by adding a monobasic acid, or a resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction.
  • Acrylic copolymer resin (d3-2) Linear alkali-soluble resin containing a carboxy group in the main chain.
  • alkali-soluble resins (d4) are alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) having carboxy groups other than alkali-soluble resins (d1), and alkali-soluble resins (d3) other than acrylic copolymer resins (d3).
  • alkali-soluble resins (d1) alkali-soluble resins (d1), epoxy (meth)acrylate resins (d2) having carboxy groups other than alkali-soluble resins (d1), and alkali-soluble resins (d3) other than acrylic copolymer resins (d3).
  • the content of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, based on the total solid content of the photosensitive resin composition of the present invention. 15% by mass or more, particularly preferably 20% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, especially Preferably, it is 25% by mass or less.
  • the amount is at least the above lower limit, the solubility of the unexposed portion in the developer tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 50% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass.
  • the content of (D) alkali-soluble resin relative to 100 parts by mass of (E) photopolymerizable compound is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and 200 parts by mass.
  • the above is more preferable.
  • it is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 600 parts by mass or less, and particularly preferably 400 parts by mass or less.
  • it is at least the above lower limit, there is a tendency that the unexposed portion has good solubility in a developer.
  • the above upper limit when it is not more than the above upper limit, it is possible to suppress excessive permeation of the developer into the exposed area, and there is a tendency that the sharpness of the image and the fine line adhesion are improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 1000 parts by mass, more preferably 100 to 800 parts by mass, even more preferably 150 to 600 parts by mass, and particularly preferably 200 to 400 parts by mass.
  • the photosensitive resin composition of the present invention contains (E) a photopolymerizable compound in terms of sensitivity and the like.
  • (E) As the photopolymerizable compound it is preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. is.
  • the sensitivity of the photosensitive resin composition tends to be high when it is equal to or higher than the lower limit, and shrinkage on curing during polymerization tends to be small when it is equal to or lower than the upper limit.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 2 to 10, more preferably 3 to 10, still more preferably 4 to 8.
  • polyfunctional ethylenic monomers examples include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Polyvalent hydroxy compounds such as polyhydroxy compounds, esters obtained by esterification reaction with unsaturated carboxylic acids and polybasic carboxylic acids, etc., and esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. .
  • ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • Acrylic acid esters of aliphatic polyhydroxy compounds such as acrylates, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylics obtained by replacing the acrylates of these exemplary compounds with methacrylates
  • Acid esters similarly, itaconic acid esters instead of itaconates, crotonic acid esters instead of clonates, and maleic acid esters instead of maleates are mentioned, and acrylic acid esters of aliphatic polyhydroxy compounds and meta-esters of aliphatic polyhydroxy compounds. Acrylic acid esters are preferred.
  • Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. and acid esters.
  • a polybasic carboxylic acid and an unsaturated carboxylic acid and an ester obtained by an esterification reaction of a polyhydric hydroxy compound are not necessarily single substances, but typical examples include acrylic acid, phthalic acid, and Condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerol.
  • polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester.
  • urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful. These may be used individually by 1 type, and may use 2 or more types together.
  • the content of the photopolymerizable compound is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 50% by mass, based on the total solid content of the photosensitive resin composition. %, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the content of the photopolymerizable compound is equal to or less than the above upper limit, there is a tendency that the penetration of the developer into the exposed area becomes moderate and good images can be obtained.
  • the lower limit of the content of (E) the photopolymerizable compound is not particularly limited, it is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the above upper and lower limits can be combined arbitrarily. For example, preferably 1 to 90% by mass, more preferably 1 to 70% by mass, still more preferably 1 to 50% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, particularly preferably is 5 to 10% by mass.
  • the photosensitive resin composition of the present invention contains (F) a photopolymerization initiator.
  • the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, an additive such as a sensitizing dye may be added for use.
  • Photopolymerization initiators include, for example, Japanese Patent Laid-Open Nos. 59-152396 and 61-151197, metallocene compounds containing titanocene compounds; Hexaarylbiimidazole derivatives described in JP-A-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl- ⁇ -amino acids such as N-phenylglycine described in JP-A-10-39503 Radical activators such as N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Examples thereof include oxime ester derivatives described in JP-A-2003-201215 and the like.
  • Titanocene derivatives include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl-1-yl), Dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl
  • Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl ) imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′ -methoxyphenyl)-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2′-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2 '-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6′′-benzofuryl)vinyl)]-1,3,4-oxadiazole , 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloro methyl)-s-triazine.
  • ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1 ,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
  • oxime ester derivatives are particularly effective in terms of sensitivity.
  • oxime ester derivatives oxime ester compounds and keto oxime ester compounds
  • having excellent sensitivity are useful.
  • oxime ester derivatives are preferred from the viewpoint of adhesion to substrates.
  • the photopolymerization initiator of the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so it is highly sensitive even in a small amount and can react with heat. It is stable against , and it is possible to design a highly sensitive photosensitive resin composition in a small amount.
  • an oxime ester compound containing an optionally substituted carbazolyl group (a group having an optionally substituted carbazole ring)
  • This structural characteristic is well expressed, which is more preferable.
  • a thin BM black matrix
  • the pigment concentration is also increasing more and more. It is particularly effective in such circumstances.
  • oxime ester-based compound examples include compounds containing a structural moiety represented by the following general formula (22), preferably oxime ester-based compounds represented by the following general formula (23).
  • R 22 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or 3 carbon atoms.
  • ⁇ 8 cycloalkanoyl group C3-C20 alkoxycarbonylalkanoyl group, C8-C20 phenoxycarbonylalkanoyl group, C3-C20 heteroaryloxycarbonylalkanoyl group, C2-C10 amino It represents an alkylcarbonyl group, an aroyl group having 7 to 20 carbon atoms, a heteroaroyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.
  • R 21a is hydrogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms , a C2-12 alkanoyl group, a C3-25 alkenoyl group, a C3-8 cycloalkanoyl group, a C7-20 aroyl group, a C1-20 heteroaroyl group, a C2 1 to 10 alkoxycarbonyl groups, aryloxycarbonyl groups having 7 to 20 carbon atoms, or cycloalkylalkyl groups having 1 to 10 carbon atoms
  • R 22a represents the same group as R 22 in formula (22).
  • R 22 in formula (22) and R 22a in formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or a cycloalkanoyl group having 3 to 8 carbon atoms. are mentioned.
  • R 21a in formula (23) is preferably an unsubstituted straight-chain alkyl group such as methyl, ethyl or propyl, or a cycloalkylalkyl group, or propyl substituted with an N-acetyl-N-acetoxyamino group. groups.
  • R 21b in formula (23) preferably includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.
  • R 21b in formula (23) is an optionally substituted carbazolyl group
  • R 21b in formula (23) is an optionally substituted carbazolyl group
  • optionally substituted aryl groups having 6 to 25 carbon atoms optionally substituted arylcarbonyl groups having 7 to 25 carbon atoms
  • optionally substituted heteroaryl groups having 5 to 25 carbon atoms substituted A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted and a nitro group is preferred.
  • a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoyl group, a naphthoyl group, a thienylcarbonyl group and a nitro group is particularly preferred. Moreover, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.
  • photopolymerization initiators for such oxime ester compounds include OXE-02 manufactured by BASF and TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power Electronics.
  • photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but are not limited to these compounds.
  • the ketoxime ester-based compound includes a compound containing a structural moiety represented by the following general formula (24), preferably a ketoxime ester-based compound represented by the following general formula (25).
  • R 24 has the same definition as R 22 in formula (22).
  • R 23a is an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms , an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a carbon number It represents a heteroaroyl group having 1 to 20 carbon atoms,
  • R 23b represents any substituent containing an aromatic or heteroaromatic ring.
  • R 24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a carbon heteroaroyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylaminocarbonyl group having 2 to 20 carbon atoms represents R 24 in formula (24) and R 24a in general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cyclo An alkanoyl group and an aroyl group having 7 to 20 carbon atoms can be mentioned.
  • R 23a in formula (25) preferably includes an unsubstituted ethyl group, propyl group, butyl group, and an ethyl group or propyl group substituted with a methoxycarbonyl group.
  • R 23b in formula (25) preferably includes an optionally substituted carbazolyl group and an optionally substituted phenylsulfide group.
  • Specific examples of the ketoxime ester compounds suitable for the present invention include compounds as exemplified below, but are not limited to these compounds.
  • photopolymerization initiators for such ketoxime ester compounds include OXE-01 manufactured by BASF Corporation and TR-PBG-305 manufactured by Changzhou Power Electronics Co., Ltd.
  • oxime ester compounds and keto oxime ester compounds are themselves known compounds.
  • is a kind of compound of One type of the photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2 -phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropy
  • the photopolymerization initiator (F) can be combined with a sensitizing dye corresponding to the wavelength of the image exposure light source for the purpose of increasing the sensitivity.
  • these sensitizing dyes include, for example, JP-A-4-221958, xanthene dyes described in JP-A-4-219756, JP-A-3-239703, JP-A-5- A coumarin dye having a heterocycle described in JP-A-289335, a 3-ketocoumarin compound described in JP-A-3-239703, a 3-ketocoumarin compound described in JP-A-5-289335, and a JP-A-6-19240
  • JP-A-6-19240 The pyrromethene dyes described above, Japanese Patent Laid-Open Nos.
  • amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred.
  • Benzophenone compounds such as diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl) benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzo
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 2% by mass or more, based on the total solid content of the photosensitive resin composition of the present invention. is 3% by mass or more, particularly preferably 4% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less, Particularly preferably, it is 8% by mass or less. Sensitivity tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that the adhesion stress with the substrate is improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, still more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
  • the content of the oxime ester compound is not particularly limited. It 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, relative to the solid content. Also, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. When the content is equal to or higher than the lower limit, the sensitivity tends to be improved, and fine line adhesion is improved.
  • the amount is not more than the above upper limit, there is a tendency that the solubility of the unexposed portion in the developing solution is improved.
  • the above upper and lower limits can be combined arbitrarily. It is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass, even more preferably 3 to 10% by mass, and particularly preferably 4 to 8% by mass.
  • the content of the sensitizing dye is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, more preferably 0 to 15% by mass, in the total solid content of the photosensitive resin composition. 10% by mass.
  • the photosensitive resin composition of the present invention may contain a surfactant for the purpose of adjusting coatability.
  • surfactants include BYK-330 (manufactured by BYK-Chemie, surface tension 24.4 mN/m), F-475 (manufactured by DIC, surface tension 25.4 mN/m), F-554 (manufactured by DIC, surface tension of 23.3 mN/m).
  • 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and ratios.
  • the content of the surfactant is not particularly limited. 05% by mass or more is more preferable, 0.1% by mass or more is even more preferable, and 0.15% by mass or more is particularly preferable. Also, it is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
  • the content is at least the above lower limit, the coating film uniformity tends to be improved and the fine line adhesion tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.05 to 0.7% by mass is more preferable, 0.1 to 0.5% by mass is more preferable, and 0.15 to 0.3% by mass is particularly preferable.
  • ⁇ Solvent> In the photosensitive resin composition of the present invention, for example, (D) an alkali-soluble resin, (E) a photopolymerizable compound and (F) a photopolymerization initiator and various materials used as necessary are dissolved in an organic solvent. Or used in a distributed state.
  • the organic solvent it is preferable to select an organic solvent having a boiling point (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) in the range of 100 to 300°C.
  • Organic solvents are more preferred.
  • organic solvents examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, and propylene glycol-t.
  • -butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl glycol monoalkyl ethers such as ethers, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
  • glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether; Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone
  • aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropi
  • Halogenated hydrocarbons such as butyl chloride, amyl chloride; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile;
  • solvents include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosolve” is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (any are also trade names).
  • organic solvents may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 100 to 250°C more preferably an organic solvent having a boiling point of 120 to 230°C.
  • Glycol alkyl ether acetates are preferable as the organic solvent because they have a good balance of coatability, surface tension, etc., and the solubility of each component of the photosensitive resin composition is relatively high.
  • glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • organic solvents that may be used in combination, glycol monoalkyl ethers are preferred, and propylene glycol monomethyl ether is preferred in view of the solubility of the components in the composition.
  • the proportion of the glycol monoalkyl ether in the organic solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.
  • an organic solvent having a boiling point of 200°C or higher (hereinafter sometimes referred to as a "high boiling point solvent”) may be used together.
  • a high boiling point solvent makes the photosensitive resin composition difficult to dry, but has the effect of preventing the uniformly dispersed state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of foreign matter defects due to the deposition and solidification of the coloring material at the tip of the slit nozzle.
  • dipropylene glycol methyl ether acetate diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene Glycol diacetate, triacetin, 1,6-hexanediol diacetate are preferred.
  • the content of the high-boiling solvent in the organic solvent is preferably 0 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass. .
  • the value is equal to or higher than the lower limit, it tends to be possible to suppress, for example, the deposition and solidification of the coloring material at the tip of the slit nozzle and the occurrence of foreign matter defects.
  • the drying temperature is set to the above upper limit or less, the drying temperature of the composition tends to be slowed, which tends to suppress the occurrence of problems such as tact failure in the reduced pressure drying process and pin marks during prebaking in the color filter manufacturing process.
  • the content of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass It is added so that it becomes the mass % or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the total solid content in the photosensitive resin composition is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass. may be added as follows.
  • ⁇ Other compounding components of the photosensitive resin composition in addition to the components described above, for example, thiols, additives, development modifiers, ultraviolet absorbers, and antioxidants can be appropriately blended.
  • the photosensitive resin composition of the present invention may contain thiols in order to increase sensitivity and improve adhesion to substrates.
  • Thiols include, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate.
  • butanediol bisthiopropionate trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane (trade name; Karenz MT BD1, manufactured by Showa Denko KK), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT
  • Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are preferred, Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are more preferred, and Karenz MT PE1 is even more preferred.
  • the content of the thiols is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, more preferably It is 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less.
  • the content is equal to or less than the above upper limit, there is a tendency that the storage stability tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, still more preferably 0.5 to 5% by mass.
  • Additives may be added to improve adhesion to the substrate.
  • examples include silane coupling agents and titanium coupling agents.
  • a silane coupling agent is particularly preferred.
  • Silane coupling agents include, for example, KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040. , Z-6043 and Z-6062 (manufactured by Dow Corning Toray).
  • One type of silane coupling agent may be used, or two or more types may be used in combination.
  • additives other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, examples of which include phosphoric acid-based additives and other additives.
  • (meth)acryloyloxy group-containing phosphates are preferred. Among them, those represented by the following general formulas (g1), (g2) and (g3) are preferable.
  • R 51 each independently represents a hydrogen atom or a methyl group
  • l and l′ each independently represent an integer of 1 to 10
  • m each independently represents 1, 2 or 3.
  • Other additives include, for example, TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesion agents may be used alone or in combination of two or more.
  • the content of the additive is not particularly limited, but the total solid content of the photosensitive resin composition is preferably 0.01% by mass or more, and 0.10% by mass. % or more, more preferably 0.50% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, and 1.5% by mass or less. % by mass or less is particularly preferred. Adhesion tends to be improved by making it more than the said lower limit. Further, when the content is set to the upper limit value or less, the developability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5.0% by mass is preferable, 0.01 to 3.0% by mass is more preferable, 0.10 to 2.0% by mass is more preferable, and 0.50 to 1.5% by mass is Especially preferred.
  • the photosensitive resin composition of the present invention can be suitably used for black matrix formation. From this point of view, it is preferable that the color is black. Moreover, it is preferable that the optical density (OD value) per 1.0 ⁇ m of film thickness of the cured coating film is 4.0 or more. It is more preferably 4.1 or more, further preferably 4.2 or more, and preferably 6.0 or less. By making it equal to or higher than the lower limit, there is a tendency that sufficient light shielding properties can be ensured. For example, 4.0 to 6.0 is preferred, 4.1 to 6.0 is more preferred, and 4.2 to 6.0 is even more preferred.
  • the optical density is the transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard.
  • the A light source defined by CIE International Commission on Illumination
  • An example of a measuring instrument that can be used to measure transmission optical density is X-Rite 361T(V) manufactured by Sakata Inx Engineering.
  • the pigment dispersion of the present invention is produced by a conventional method.
  • the pigment is preferably dispersed in advance using, for example, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, or homogenizer. Since the pigment (A) is finely divided by the dispersion treatment, the application properties of the photosensitive resin composition are improved.
  • A When a black pigment is used as the pigment, it contributes to the improvement of the light shielding ability.
  • Dispersion treatment is usually carried out in a system in which (A) a pigment, (B) a dispersant, (C) a sulfonic acid group-containing compound, a solvent, and optionally (D) some or all of an alkali-soluble resin are used in combination.
  • A a pigment
  • B a dispersant
  • C a sulfonic acid group-containing compound
  • solvent a solvent
  • D some or all of an alkali-soluble resin
  • the temperature condition of the dispersion treatment is preferably 0°C to 100°C, more preferably room temperature (25°C) to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate.
  • the aim of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) of the photosensitive resin composition is in the range of 100-200.
  • the dispersion treatment is sufficient, residual coarse pigment (coloring material) particles are suppressed, and sufficient developability, adhesion, and resolution are obtained. easy to get Further, when the 20-degree specular gloss value is 200 or less, the pigment is not excessively crushed, the production of a large number of ultrafine particles is suppressed, and the dispersion stability is less likely to be impaired.
  • the photosensitive resin composition of the present invention is produced by a conventional method.
  • the ink obtained by the dispersion treatment described above and other components contained in the photosensitive resin composition can be mixed to form a uniform solution.
  • fine dust is often mixed in the liquid, so it is desirable to filter the obtained photosensitive resin composition with a filter or the like.
  • the cured product of the invention can be obtained by curing the photosensitive resin composition of the invention.
  • a cured product obtained by curing the photosensitive resin composition of the present invention can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a colored spacer.
  • the black matrix of the invention consists of the cured product of the invention.
  • the material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength.
  • a transparent substrate is used.
  • Materials for the transparent substrate include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy resins, unsaturated polyester resins, Examples include thermosetting resin sheets such as poly(meth)acrylic resins and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resin are preferable.
  • a transparent electrode such as ITO or IZO may be deposited on the surface of the substrate. Other than the transparent substrate, a transparent electrode may be formed on the TFT array.
  • the support may be subjected, if necessary, to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, and thin film formation treatment using various resins such as silane coupling agents and urethane resins. may be performed.
  • the thickness of the support is preferably 0.05-10 mm, more preferably 0.1-7 mm.
  • the film thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition is applied onto a transparent substrate, dried, and then the photosensitive resin composition is applied and dried.
  • a black matrix can be formed by imagewise exposure through a photomask placed on a transparent substrate, development, and thermal curing or photocuring as necessary.
  • the coating of the photosensitive resin composition for the black matrix onto the transparent substrate can be performed by, for example, spinner method, wire bar method, flow coating method, It can be carried out by a die coating method, a roll coating method, or a spray coating method.
  • the die-coating method is preferable from the viewpoints that the amount of the coating liquid used is significantly reduced, and the mist that adheres when the spin-coating method is used does not have an effect, and the generation of foreign matter is suppressed.
  • the thickness of the coating film after drying is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m, even more preferably 1 to 4 ⁇ m.
  • the conditions for heat drying can be appropriately selected according to the type of organic solvent, the performance of the dryer to be used, and the like.
  • the temperature is 40 to 200° C. for 15 seconds to 5 minutes, more preferably 50 to 130° C. for 30 seconds to 3 minutes.
  • Imagewise exposure is carried out by overlaying a negative mask pattern on the coating film of the photosensitive resin composition and irradiating light of wavelengths from the ultraviolet region to the visible region through this mask pattern. can be done.
  • the exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film.
  • the light source used for the above image exposure is not particularly limited.
  • Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and carbon arcs.
  • An optical filter can also be used when using it by irradiating the light of a specific wavelength.
  • the black matrix of the present invention is prepared by subjecting a coating film made of a photosensitive resin composition to imagewise exposure with the light source described above, followed by an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.
  • the development used can be used to form an image on the substrate.
  • This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes and pigments.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine , mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. compound. These alkaline compounds may be used singly or in combination of two or more.
  • TMAH tetramethylammonium hydroxide
  • surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters
  • Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate
  • organic solvents examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the developing temperature is preferably 10 to 50°C, more preferably 15 to 45°C, even more preferably 20 to 40°C.
  • the development method may be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
  • the substrate after development is subjected to heat curing treatment or photocuring treatment, preferably heat curing treatment.
  • the temperature is preferably 100-280°C, more preferably 150-250°C.
  • the time is preferably 5 to 60 minutes.
  • the height of the black matrix formed as described above is preferably 0.5 to 5 ⁇ m, more preferably 0.8 to 4 ⁇ m.
  • a photosensitive resin composition containing a coloring material of one of red, green, and blue is applied in the same process as (3-1) to (3-5) above, and dried. After that, a photomask is overlaid on the coating film, imagewise exposure through the photomask, development, and if necessary, thermal curing or photocuring are performed to form a pixel image, thereby forming a colored layer.
  • a color filter can be formed by performing this operation for each of the three photosensitive resin compositions of red, green, and blue (the order may be arbitrary).
  • the photosensitive resin composition of the present invention can also be used as a photosensitive resin composition for colored spacers in addition to the black matrix.
  • the TFTs may malfunction as switching elements due to light incident on the TFTs.
  • Colored spacers are used to prevent this.
  • JP-A-2004-110003 describes that the spacer is light-shielding.
  • the colored spacers can be formed in the same manner as the black matrix described above, except that a mask for colored spacers is used.
  • the color filter is used as a part of a color display, a liquid crystal display device, or the like by forming a transparent electrode such as ITO on an image as it is.
  • a transparent electrode such as ITO
  • a top coat layer such as polyamide or polyimide may be provided on the image, if necessary.
  • IPS mode planar orientation driving system
  • the image display device of the present invention has the cured product of the present invention.
  • the image display device is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display.
  • the liquid crystal display device of the present invention has the cured product of the present invention, particularly the black matrix, and the order and positions of forming the color pixels and the black matrix are not particularly limited.
  • an alignment film is formed on a color filter, spacers are sprinkled on the alignment film, and then a counter substrate is attached to form a liquid crystal cell.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and/or a flexographic printing method can be employed for forming the alignment film, and the thickness of the alignment film may be several tens of nm.
  • the surface After hardening the alignment film by heat baking, the surface may be processed by irradiating with ultraviolet rays or by treatment with a rubbing cloth so as to obtain a surface state capable of adjusting the tilt of the liquid crystal.
  • a spacer having a size corresponding to the gap (clearance) with the counter substrate is used, and a spacer of 2 to 8 ⁇ m is suitable.
  • a photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer.
  • An array substrate can be used as the opposing substrate, and a TFT (thin film transistor) substrate is particularly suitable.
  • the gap between the substrate and the opposing substrate may be 2 to 8 ⁇ m, depending on the application of the liquid crystal display device.
  • the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
  • the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell.
  • the degree of pressure reduction in the liquid crystal cell is preferably 1 ⁇ 10 -2 to 1 ⁇ 10 -7 Pa, more preferably 1 ⁇ 10 -3 to 1 ⁇ 10 -6 Pa.
  • the heating temperature is preferably 30 to 100°C, more preferably 50 to 90°C. Heating and holding at reduced pressure may be for 10 to 60 minutes, and then immersed in liquid crystal.
  • a liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.
  • the type of liquid crystal is not particularly limited.
  • it may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, or a polycyclic compound, such as a lyotropic liquid crystal or a thermotropic liquid crystal.
  • Thermotropic liquid crystals may be, for example, nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, or the like.
  • Organic EL display The organic EL display of the invention is produced using the color filter of the invention.
  • a color filter is prepared by forming a resin black matrix (not shown) provided between the pixels 20, and an organic light emitter 500 is formed on the color filter with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween.
  • the organic EL element 100 can be produced by laminating the .
  • At least one of the pixels 20 and the resin black matrix is manufactured using the photosensitive resin composition of the present invention.
  • the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light emitting layer 53, the electron injection layer 54, and the cathode 55 are sequentially formed on the upper surface of the color filter.
  • organic EL element 100 for example, the method described in "Organic EL Display” (Ohmsha, Aug. 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can produce an organic EL display.
  • the color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic dianhydride
  • THPA tetrahydrophthalic anhydride
  • the constituent components of the pigment dispersion liquid and the photosensitive resin composition used in the following examples and comparative examples are as follows.
  • Sulfonic acid group-containing compound A electrical conductivity 2080 ⁇ S/cm, acid value 80 mgKOH/g Sulfonic acid group-containing compound B: electrical conductivity 5100 ⁇ S/cm, acid value 81 mgKOH/g Sulfonic acid group-containing compound C: electrical conductivity 9012 ⁇ S/cm, acid value 83 mgKOH/g Sulfonic acid group-containing compound D: electrical conductivity 1420 ⁇ S/cm, acid value 40 mgKOH/g
  • Compound E C.I. I. Pigment Blue 15:6 (electrical conductivity 0 ⁇ S/cm, acid value 0 mgKOH/g)
  • Alkali-soluble resin-1 Resin described in Synthesis Example
  • DPHA "KAYARAD DPHA” (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
  • TR-PBG-304 "TR-PBG-304" (an oxime ester compound having a carbazole skeleton) manufactured by Changzhou Power Electronics New Materials Co., Ltd.
  • X-12-1048 Shin-Etsu Chemical Co., Ltd. "X-12-1048" (polyfunctional acrylic silane)
  • a photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 ⁇ m, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom.
  • a photomask having a line width opening of 1 ⁇ m to 20 ⁇ m in increments of 1 ⁇ m is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
  • a photosensitive resin composition was coated on a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 ⁇ m, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. bottom.
  • a photomask having a line width opening of 1 ⁇ m to 20 ⁇ m in increments of 1 ⁇ m is used as a photomask for the resulting coating film, and ultraviolet rays having a wavelength of 365 nm and an intensity of 60 mW/cm 2 are used to expose the coating film. Exposure processing was carried out so as to obtain 40 mJ/cm 2 .
  • a substrate was prepared in the same manner as the thin line adhesion evaluation substrate, and the linearity of the pattern corresponding to the 6 ⁇ m opening of the photomask was measured using an optical microscope.
  • Example 1 From Example 1, Example 2, and Comparative Example 1, when the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S/cm or less and the acid value is 40 mgKOH/g or more, the solubility in development is excellent and the fine line adhesion is good. It was shown to be superior in terms of performance. On the other hand, when the electrical conductivity of (C) the sulfonic acid group-containing compound exceeds 9000 ⁇ S/cm, that is, when the electrical conductivity increases, the amount of free acid due to poor pigment adsorption of the (C) sulfonic acid group-containing compound increases. It is thought that the dissolution time was shortened and the undercut was emphasized, which deteriorated the fine wire adhesion.
  • Example 3 and Comparative Example 1 if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S / cm or less, the amount of (C) the sulfonic acid group-containing compound relative to the amount of pigment Even when the content was increased from 2% to 10%, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly. From Example 1, Example 4 and Comparative Example 1, if the electrical conductivity of (C) the sulfonic acid group-containing compound is 9000 ⁇ S / cm or less, the amount of dispersant is changed from 20% to 25% with respect to the amount of pigment. Even if it was increased, the fine wire adhesion did not deteriorate, and the dissolution rate did not change significantly.
  • Example 1 and Comparative Example 2 when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 ⁇ S/cm, the acid value around the pigment is significantly decreased, resulting in a long dissolution time and poor fine line adhesion. was shown. It was also shown that the linearity deteriorated and it became difficult to form thin lines. From Example 1, Comparative Example 2, and Comparative Example 3, when the electrical conductivity of (C) the sulfonic acid group-containing compound is less than 2000 ⁇ S/cm and the acid value is less than 40 mgKOH/g, the pigment adsorption capacity is lost.
  • the sulfonic acid group-containing compound has an electrical conductivity of 2000 ⁇ S/cm or more and 9000 ⁇ S/cm or less and an acid value of 40 mgKOH/g or more, thereby minimizing the influence of the free acid. It was shown that the fine wire adhesion and linearity were improved, and the amount of change in dissolution time could be reduced.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Theoretical Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Materials For Photolithography (AREA)
PCT/JP2022/038423 2021-10-20 2022-10-14 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置 Ceased WO2023068201A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2023554654A JPWO2023068201A1 (https=) 2021-10-20 2022-10-14
KR1020247012626A KR20240090190A (ko) 2021-10-20 2022-10-14 안료 분산액, 감광성 수지 조성물, 경화물, 블랙 매트릭스 및 화상 표시 장치
CN202280069849.7A CN118103464A (zh) 2021-10-20 2022-10-14 颜料分散液、感光性树脂组合物、固化物、黑色矩阵和图像显示装置

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021171566 2021-10-20
JP2021-171566 2021-10-20
JP2021-199773 2021-12-09
JP2021199773 2021-12-09

Publications (1)

Publication Number Publication Date
WO2023068201A1 true WO2023068201A1 (ja) 2023-04-27

Family

ID=86059287

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/038423 Ceased WO2023068201A1 (ja) 2021-10-20 2022-10-14 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置

Country Status (4)

Country Link
JP (1) JPWO2023068201A1 (https=)
KR (1) KR20240090190A (https=)
TW (1) TW202323447A (https=)
WO (1) WO2023068201A1 (https=)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015084086A (ja) * 2013-09-20 2015-04-30 三菱化学株式会社 感光性樹脂組成物、それを硬化させてなる硬化物、ブラックマトリックス及び画像表示装置
WO2016002911A1 (ja) * 2014-07-04 2016-01-07 三菱化学株式会社 樹脂、感光性樹脂組成物、硬化物、カラーフィルタ及び画像表示装置
WO2016006669A1 (ja) * 2014-07-11 2016-01-14 三菱化学株式会社 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP2016079245A (ja) * 2014-10-14 2016-05-16 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物
JP2018184575A (ja) * 2017-04-27 2018-11-22 コニカミノルタ株式会社 活性光線硬化型インクジェットインクおよびその製造方法
JP2019082533A (ja) * 2017-10-30 2019-05-30 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物及びそれを含有するブラックマトリックス用顔料分散レジスト組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5108300B2 (ja) 2006-12-28 2012-12-26 新日鉄住金化学株式会社 感光性樹脂組成物及びそれを用いたカラーフィルター

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015084086A (ja) * 2013-09-20 2015-04-30 三菱化学株式会社 感光性樹脂組成物、それを硬化させてなる硬化物、ブラックマトリックス及び画像表示装置
WO2016002911A1 (ja) * 2014-07-04 2016-01-07 三菱化学株式会社 樹脂、感光性樹脂組成物、硬化物、カラーフィルタ及び画像表示装置
WO2016006669A1 (ja) * 2014-07-11 2016-01-14 三菱化学株式会社 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP2016079245A (ja) * 2014-10-14 2016-05-16 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物
JP2018184575A (ja) * 2017-04-27 2018-11-22 コニカミノルタ株式会社 活性光線硬化型インクジェットインクおよびその製造方法
JP2019082533A (ja) * 2017-10-30 2019-05-30 サカタインクス株式会社 ブラックマトリックス用顔料分散組成物及びそれを含有するブラックマトリックス用顔料分散レジスト組成物

Also Published As

Publication number Publication date
KR20240090190A (ko) 2024-06-21
JPWO2023068201A1 (https=) 2023-04-27
TW202323447A (zh) 2023-06-16

Similar Documents

Publication Publication Date Title
JP7283519B2 (ja) 感光性樹脂組成物、硬化物及び画像表示装置
JP6361838B2 (ja) 感光性着色組成物、硬化物、ブラックマトリクス、着色スペーサー及び画像表示装置
JP5957952B2 (ja) 感光性着色樹脂組成物、及びカラーフィルタ、及び液晶表示装置
JP2013167687A (ja) 感光性着色樹脂組成物、及びカラーフィルタ、及び液晶表示装置
JP2013011845A (ja) カラーフィルタ用感光性着色樹脂組成物、カラーフィルタ、液晶表示装置及び有機ｅｌディスプレイ
JP7188115B2 (ja) アルカリ可溶性樹脂、感光性樹脂組成物、硬化物、及び画像表示装置
JP2013195681A (ja) 感光性樹脂組成物、カラーフィルタ、液晶表示装置、及び有機ｅｌディスプレイ
JP2022108724A (ja) 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP7120234B2 (ja) 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP2013065000A (ja) 感光性着色樹脂組成物、カラーフィルタ、及び液晶表示装置
KR20230117134A (ko) 감광성 수지 조성물, 경화물, 블랙 매트릭스 및 화상 표시 장치
JP6607054B2 (ja) 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP2022063445A (ja) 感光性着色組成物、硬化物、ブラックマトリックス及び画像表示装置
WO2023068201A1 (ja) 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
JP7779265B2 (ja) カルボキシ基含有樹脂の製造方法及びカルボキシ基含有樹脂の分子量の制御方法
WO2023182350A1 (ja) 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス、画像表示装置、及び顔料分散液の製造方法
WO2024214806A1 (ja) 顔料分散液、感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
WO2025192684A1 (ja) 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置
CN118103464A (zh) 颜料分散液、感光性树脂组合物、固化物、黑色矩阵和图像显示装置
WO2022091905A1 (ja) カルボキシ基含有樹脂含有液の製造方法及びカルボキシ基含有樹脂の安定化方法
JP2022060893A (ja) オキシムエステル系化合物の製造方法及び感光性樹脂組成物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22883505

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023554654

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280069849.7

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22883505

Country of ref document: EP

Kind code of ref document: A1