WO2016143878A1 - Composition colorante photosensible pour former un espaceur coloré, produit durci, espaceur coloré, et dispositif d'affichage d'image - Google Patents

Composition colorante photosensible pour former un espaceur coloré, produit durci, espaceur coloré, et dispositif d'affichage d'image Download PDF

Info

Publication number
WO2016143878A1
WO2016143878A1 PCT/JP2016/057678 JP2016057678W WO2016143878A1 WO 2016143878 A1 WO2016143878 A1 WO 2016143878A1 JP 2016057678 W JP2016057678 W JP 2016057678W WO 2016143878 A1 WO2016143878 A1 WO 2016143878A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
pigment
mass
coloring composition
photosensitive coloring
Prior art date
Application number
PCT/JP2016/057678
Other languages
English (en)
Japanese (ja)
Inventor
敦哉 伊藤
善秀 小川
大津　猛
麗華 裴
Original Assignee
三菱化学株式会社
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=56879478&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2016143878(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Priority to KR1020177025400A priority Critical patent/KR102491215B1/ko
Priority to CN201680014325.2A priority patent/CN107407881A/zh
Priority to JP2017505412A priority patent/JP7131907B2/ja
Publication of WO2016143878A1 publication Critical patent/WO2016143878A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C09B57/00—Other synthetic dyes of known constitution
    • 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
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties
    • 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
    • G03F7/09—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

Definitions

  • the present invention relates to a photosensitive coloring composition and the like. Specifically, the present invention relates to a photosensitive coloring composition that is preferably used for forming a colored spacer or the like in a color filter such as a liquid crystal display, a coloring spacer obtained by curing the photosensitive coloring composition, and an image display device including the coloring spacer. .
  • Liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off the voltage to the liquid crystal.
  • each member constituting the LCD cell is often formed by a method using a photosensitive composition represented by a photolithography method. This photosensitive composition tends to form a fine structure and is easy to process a substrate for a large screen, and its application range tends to further expand in the future.
  • Patent Document 1 describes a method using a light-shielding spacer (colored spacer).
  • Patent Document 2 discloses a pigment using a plurality of types of organic coloring pigments
  • Patent Document 4 discloses a pigment using an organic black pigment.
  • Patent Document 5 describes the use of a specific oxime ester compound as a highly sensitive photopolymerization initiator for the purpose of increasing curability in color filter resist applications.
  • the method for increasing the light shielding property include a method using a pigment having a high light shielding property and a method for increasing the pigment content ratio in the photosensitive coloring composition.
  • Patent Document 5 describes using a specific oxime ester compound as a photopolymerization initiator for a color resist.
  • Patent Document 5 does not describe or suggest that this oxime ester compound is used as a photopolymerization initiator of a photosensitive coloring composition for forming a colored spacer. Therefore, it is unclear how this oxime ester compound acts when used as a photopolymerization initiator for a photosensitive coloring composition for forming a colored spacer.
  • This invention is made
  • the above-mentioned problems can be solved by using a specific oxime ester compound as a photopolymerization initiator in the photosensitive coloring composition. And found the present invention.
  • At least one of R 1 and R 4 has a —OR 7 group as a substituent.
  • R 7 represents a halogenoalkyl group.
  • X represents a direct bond or a carbonyl group.
  • Z represents a direct bond or a carbonyl group.
  • the (a) colorant contains at least one selected from the group consisting of a red pigment and an orange pigment and at least one selected from the group consisting of a blue pigment and a purple pigment.
  • the red pigment is (1) below, the orange pigment is (2) below, the blue pigment is (3) below, and the purple pigment is (4) below.
  • the content ratio of at least one pigment selected from the group consisting of a red pigment and an orange pigment with respect to 100 parts by mass of the colorant (a) selected from at least one selected from CI Pigment Bio Red 23 and 29 is 1 part by mass.
  • the content ratio of at least one pigment selected from the group consisting of a blue pigment and a purple pigment with respect to 100 parts by mass of the colorant (a) is 20 parts by mass or more and 90 parts by mass or less.
  • R 11 and R 16 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the organic pigment contains a blue pigment and a purple pigment. object.
  • An image display device comprising the colored spacer according to [17].
  • (meth) acryl means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
  • (co) polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer).
  • acid (anhydride) means to include both acids and anhydrides.
  • acrylic resin means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
  • the term “monomer” is a term corresponding to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a monomer (monomer) in a narrow sense. It is.
  • total solid content means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
  • weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the “amine value” means an 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. It is. The measuring method will be described later.
  • the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
  • the photosensitive coloring composition of the present invention is (A) Colorant (b) Alkali-soluble resin (c) Photopolymerization initiator (d) Ethylenically unsaturated compound (e) Solvent (f) A dispersant is contained as an essential component.
  • the photosensitive coloring composition of the present invention may further comprise an adhesion improver such as a silane coupling agent, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment, if necessary. It contains other compounding components such as derivatives, and each compounding component is usually used in a state dissolved or dispersed in a solvent.
  • the photosensitive coloring composition of the present invention has a high light-shielding property and can form a pattern with excellent surface smoothness, it can be preferably used for forming a colored spacer, that is, a photosensitive property for forming a colored spacer. It can be suitably used as a coloring composition.
  • characteristics such as light-shielding properties and surface smoothness are required in applications other than colored spacers such as a partition wall of a light emitting portion of an organic EL display device, particularly a colored partition wall (colored bank). It can be used without being limited to the spacer.
  • a coloring spacer use and uses other than a coloring spacer are demonstrated collectively.
  • the colorant is selected from the group consisting of at least one selected from the group consisting of a red pigment and an orange pigment and from the group consisting of a blue pigment and a purple pigment.
  • the photopolymerization initiator contains an oxime ester compound represented by the formula (I) described later.
  • the “photosensitive coloring composition of the present invention” refers to all of the photosensitive coloring compositions according to the first to fourth embodiments.
  • the colorant (a) used in the photosensitive coloring composition according to the first aspect of the present invention is selected from the group consisting of at least one selected from the group consisting of red pigments and orange pigments, and the group consisting of blue pigments and purple pigments. Containing at least one species.
  • the photosensitive coloring composition which concerns on the 1st aspect of this invention can achieve high light-shielding property by containing a specific organic coloring pigment.
  • a pigment As the colorant, and as the pigment, an inorganic pigment or an organic pigment may be used. It is preferable to use an organic pigment from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to easily control the shape and level difference.
  • pigments are not particularly limited.
  • various inorganic pigments can be used in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene.
  • pigment numbers such as “CI Pigment Red 2” mentioned below mean the color index (CI).
  • C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
  • C.I. I. Pigment Red 177, 254, 272 is preferably used.
  • a red pigment having a low ultraviolet absorption rate it is preferable to use a red pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. More preferably, CI pigment red 254 and 272 are used.
  • 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.
  • C.I. I. And CI pigment oranges 38 and 71.
  • C.I. I. It is preferable to use CI Pigment Orange 43, 64, 72.
  • an orange pigment having a low ultraviolet absorption rate it is preferable to use an orange pigment having a low ultraviolet absorption rate. From this point of view, C.I. I. More preferably, CI pigment oranges 64 and 72 are used.
  • C.I. I. Pigment Blue 1 As blue pigment, 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.
  • C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used.
  • a blue pigment having a low ultraviolet absorption rate is preferable to use. From this point of view, C.I. I. More preferably, CI Pigment Blue 60 is used.
  • C.I. I. Pigment violet 19 23, more preferably C.I. I. And CI Pigment Violet 23.
  • C.I. I. Pigment violet 23 and 29 are preferably used.
  • a violet pigment having a low ultraviolet absorption rate it is preferable to use. From this point of view, C.I. I. More preferably, pigment violet 29 is used.
  • organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments and purple pigments include green pigments and yellow pigments.
  • Green pigments include 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. Of these, C.I. I. And CI Pigment Green 7 and 36.
  • ⁇ As yellow pigment C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183,
  • 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.
  • Red pigment C.I. I. Pigment Red 177, 254, 272
  • Orange pigment C.I. I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. I. Pigment Blue 15: 6, 60 Purple pigment: C.I. I. Pigment Violet 23, 29
  • the red pigment is preferably the following (1)
  • the orange pigment is preferably the following (2)
  • the blue pigment is the following ( 3) is preferable
  • the purple pigment is preferably the following (4).
  • C.I. I. At least one selected from CI Pigment Red 177 and 254 (2)
  • C.I. I. At least one selected from Pigment Orange 43 and 64 (3)
  • C.I. I. Pigment blue 15: 6, at least one selected from 60 (4)
  • C.I. I. At least one selected from Pigment Bio Red 23 and 29
  • a black color material can be further used.
  • the black color materials it is preferable to use an organic black pigment from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and controlling the shape and level difference by suppressing the absorption of ultraviolet rays. From the viewpoint of properties, it is preferable to use an organic black pigment which is a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
  • R 11 and R 16 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
  • the compound represented by general formula (1) When the compound represented by general formula (1) is anionic, its charge can be any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal.
  • the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably a similar salt.
  • R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are preferably each independently a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
  • R 13 and R 18 are preferably independently of each other a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 — , more preferably a hydrogen atom or SO 3 H.
  • R 11 and R 16 are preferably each independently a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.
  • At least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, and more preferably R 11 is the same as R 16 ; R 12 is the same as R 17 ; R 13 is the same as R 18 ; R 14 is the same as R 19 ; and R 15 is the same as R 20 Are the same.
  • the alkyl group having 1 to 12 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2- An ethylhexyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group;
  • Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tuzyl group, norbornyl group, bornyl group, norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.
  • alkenyl group having 2 to 12 carbon atoms examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene.
  • Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, , 4-Cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -Yl group, 7,7-dimethyl-2,4-norcaradien-3-yl group or camphenyl group.
  • alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl.
  • the organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2).
  • organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
  • This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later.
  • dispersibility and storage stability may be improved.
  • Examples of the black color material other than the organic black pigment represented by the general formula (1) include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black. Is mentioned. Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. Examples of carbon black include the following carbon black.
  • Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color 1 Black Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
  • Colombian Carbon Corporation Colombian Carbon Corporation: RAVEN (registered trademark, the same shall apply hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RA101000RA, V1020RA RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
  • Carbon black coated with resin may be used.
  • Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance.
  • carbon black coated with the resin for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
  • Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
  • the total content of Na and Ca is preferably 100 ppm or less.
  • Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe.
  • the ash content of etc. is contained on the order of percent.
  • Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.
  • the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained.
  • Average particle size means number average particle size. Photographs taken with tens of thousands of magnifications by electron microscope observation are taken in several fields of view, and particle image analysis in which about 2000 to 3000 particles of these photographs are measured by an image processing apparatus. This means the equivalent circle diameter obtained by.
  • the method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and the resin, and then the resulting granular material is separated and heated to remove the remaining solvent and water; 3.
  • a carboxylic acid such as maleic acid or fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and then a resin is added thereto.
  • dry blending method A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension.
  • a method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.
  • the type of resin to be coated is not particularly limited, but a synthetic resin is common, and a resin having a benzene ring in its structure has a stronger function as an amphoteric surfactant. From the viewpoints of stability and dispersion stability.
  • thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene.
  • Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used.
  • the coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and there is a tendency that the coating can be made sufficiently by setting the amount to the lower limit value or more. On the other hand, by setting it to the upper limit value or less, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.
  • the carbon black thus coated with the resin can be used as a light shielding material for a colored spacer according to a conventional method, and a color filter having this colored spacer as a constituent element can be prepared by a conventional method.
  • a colored spacer having a high light shielding rate and a low surface reflectance can be achieved at a low cost. It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.
  • dyes may be used.
  • the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes 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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
  • 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 etc. are mentioned.
  • Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
  • These pigments are preferably used in a dispersed state so that the average particle size is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less.
  • the standard of the average particle diameter is the number of pigment particles.
  • the (a) colorant used in the photosensitive coloring composition according to the second aspect of the present invention is a compound represented by the general formula (1), a geometric isomer thereof, a salt thereof, or a geometric isomerism thereof. Contains organic black pigments that are salt of the body. Thus, it is considered that a low dielectric constant and a high light blocking ratio can be realized by including a specific organic black pigment.
  • the colorant used in the second aspect of the present invention may contain other colorants in addition to the organic black pigment.
  • the other colorant it is preferable to use a pigment.
  • the pigment may be an organic pigment or an inorganic pigment, but it suppresses the decrease in the voltage holding ratio of the liquid crystal and suppresses the absorption of ultraviolet rays. From the viewpoint of facilitating control of the shape and level difference, it is more preferable to use an organic pigment.
  • the organic pigment those mentioned in the first embodiment can be used.
  • black color materials can be used.
  • black color materials it is represented by the general formula (1) from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and controlling the shape and level difference by suppressing the absorption of ultraviolet rays.
  • organic black pigments include aniline black, perylene black, and cyanine black.
  • an inorganic black pigment can be used.
  • the inorganic black pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, and the like.
  • carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics.
  • carbon black what was mentioned in the 1st aspect can be used.
  • other colorants such as dyes mentioned in the first embodiment can also be used.
  • the (a) colorant used in the photosensitive coloring composition according to the third aspect of the present invention contains an organic pigment and carbon black. As described above, it is easy to control the shape and the level difference by using an organic pigment that absorbs less ultraviolet light, and it is possible to achieve a high light shielding property by using carbon black in addition to the organic pigment.
  • the kind of the organic pigment is not particularly limited, but it is preferable to contain at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a purple pigment from the viewpoint of adhesion.
  • a red pigment, orange pigment, blue pigment, and purple pigment those described in the first embodiment can be used.
  • At least one of the following (1) to (4) is contained from the viewpoint of light shielding properties and control of shape and level difference.
  • a blue pigment and / or a violet pigment from the viewpoint of light shielding properties in the visible region, particularly in the long wavelength region.
  • the absorption spectrum of carbon black has a decreasing absorbance from short wavelength to long wavelength, and the absorbance in the ultraviolet region is higher than that of organic pigments. From this point of view, it is preferable to use a blue pigment and / or purple pigment and carbon black in combination, and it is more preferable to use a blue pigment and purple pigment and carbon black in combination.
  • the organic pigment preferably contains an organic black pigment.
  • the organic black pigment those mentioned in the first embodiment can be used.
  • the other organic coloring pigment mentioned in the 1st aspect another black color material, dye, etc. can also be used.
  • the colorant used in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect of the present invention is not particularly limited as long as a desired colored spacer can be formed.
  • a desired colored spacer can be formed.
  • at least one selected from the group consisting of a red pigment and an orange pigment described above as the first embodiment, a blue pigment and a purple color It is preferable to contain at least one selected from the group consisting of pigments.
  • the (a) colorant used in the photosensitive coloring composition according to the first aspect is used as the (a) colorant used in the photosensitive coloring composition for forming the colored spacer according to the fourth aspect.
  • the (a) colorant used with the photosensitive coloring composition which concerns on the 2nd or 3rd aspect can also be applied.
  • the photosensitive coloring composition for forming a colored spacer it is preferable that at least a black color material is contained, and at least carbon black is contained from the viewpoint of light shielding properties. Is more preferable.
  • Carbon black and an organic black pigment may be used in combination from the viewpoints of light shielding properties, suppression of a decrease in voltage holding ratio of liquid crystal, and control of shape and level difference.
  • a preferable value in the photosensitive coloring composition of the present invention described later can be adopted as the blending amount of these coloring agents.
  • it can also adjust suitably according to the optical density requested
  • the values described in Japanese Patent Application Laid-Open No. 2014-146029, International Publication No. 2013/179237, Japanese Patent Application Laid-Open No. 2011-107707, and the like can also be adopted.
  • the (b) alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group.
  • an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin is used.
  • a urethane resin, a novolac resin, a polyvinylphenol resin, and the like can be given.
  • an epoxy (meth) acrylate resin and an acrylic resin are preferable. These can be used individually by 1 type or in mixture of multiple types.
  • the alkali-soluble resin (b) used in the present invention is particularly the following alkali-soluble resin (b1) and / or alkali-soluble resin (b2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). Is preferably used from the viewpoint of excellent plate-making property.
  • epoxy resin used as a raw material for example, bisphenol A type epoxy resin (for example, “Epicoat (registered trademark; the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • bisphenol A type epoxy resin for example, “Epicoat (registered trademark; the same applies hereinafter) 828
  • Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd.
  • NC-3000 and epoxy resin represented by the following general formula (B4) include“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • a represents an average value and represents a number from 0 to 10.
  • R 111 represents any of 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, and a biphenyl group.
  • a plurality of R 111 present in one molecule may be the same or different.
  • R 121 represents any one of 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, and a biphenyl group.
  • a plurality of R 121 present in one molecule may be the same or different.
  • X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, one or more adamantane structures are included in the molecular structure.
  • c represents an integer of 2 or 3.
  • R 131 to R 134 and R 135 to R 137 are each independently an adamantyl group, a hydrogen atom, or a substituent, which may have a substituent. And an alkyl group having 1 to 12 carbon atoms which may have a phenyl group which may have a substituent. * Indicates a bond.
  • p and q each independently represent an integer of 0 to 4
  • R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represents an integer of 0 or more.
  • an epoxy resin represented by any one of the general formulas (B1) to (B4) it is preferable to use an epoxy resin represented by any one of the general formulas (B1) to (B4).
  • Examples of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth) acryl
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
  • a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
  • an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can.
  • esterification catalyst used here tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
  • the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof.
  • Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
  • a known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid having a carboxyl group to epoxy resin.
  • the target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction.
  • the addition amount of the polybasic acid and / or its anhydride component is such that the acid value of the carboxyl group-containing epoxy (meth) acrylate resin to be produced is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 50 mgKOH / g or more. Further, it is preferably about 150 mgKOH / g or less, more preferably 140 mgKOH / g or less, and still more preferably 120 mgKOH / g. There exists a tendency for alkali developability to become favorable by setting it as the said lower limit or more, and there exists a tendency for hardening performance to become favorable by setting it as the said upper limit or less.
  • transduced polyfunctional alcohol such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce
  • the carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin with an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol.
  • the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating.
  • carboxyl group-containing epoxy (meth) acrylate resin one kind may be used alone, or two or more kinds may be mixed and used.
  • carboxyl group-containing epoxy (meth) acrylate resin may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination.
  • the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in (b) the alkali-soluble resin is 50% by mass or more, particularly 80% by mass or more.
  • binder resin which can be used together with a carboxyl group-containing epoxy (meth) acrylate resin, What is necessary is just to select from the resin normally used for the photosensitive coloring composition.
  • all other binder resins may be used alone or in combination of two or more.
  • acrylic resin examples include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”) and other copolymerizable ethylenically unsaturated monomers. Examples thereof include a copolymer with a monomer (hereinafter referred to as “unsaturated monomer (b2)”).
  • the unsaturated monomer (b1) examples include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Acid, itaconic anhydride, citraconic acid, citraconic anhydride, unsaturated dicarboxylic acid such as mesaconic acid or anhydride thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl]; having carboxy groups and hydroxyl groups at both ends such as ⁇ -carboxypolycaprolactone mono (meth) acrylate Examples thereof include mono (meth) acrylates of polymers; p-vinylbenzoic acid and the like. These uns
  • Examples of the unsaturated monomer (b2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ - Aromatic vinyl compounds such as methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
  • N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
  • styrene ⁇ -methylstyrene
  • p-hydroxystyrene p-hydroxy- ⁇ -
  • Aromatic vinyl compounds such as methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
  • Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane
  • a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
  • These unsaturated monomers (b2) can be used alone or in admixture of two or more.
  • copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japan Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japan Examples thereof include copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728.
  • the photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
  • R 1 represents an aromatic ring group which may have a substituent.
  • R 2 represents an alkanoyl group which may have a substituent, or an aryloyl group which may have a substituent.
  • R 3 represents a hydrogen atom or an alkyl group which may have a substituent.
  • R 4 represents an aromatic ring group which may have a substituent.
  • R 5 and R 6 each independently represents a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, at least one of R 5 and R 6 is a naphthalene ring which may have a substituent.
  • At least one of R 1 and R 4 has a —OR 7 group as a substituent.
  • R 7 represents a halogenoalkyl group.
  • X represents a direct bond or a carbonyl group.
  • Z represents a direct bond or a carbonyl group.
  • Examples of the aromatic ring group for R 1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is preferably 30 or less, more preferably 12 or less, and even more preferably 8 or less. Moreover, it is 4 or more normally, and it is preferable that it is 6 or more.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group (an alkyl group in which some or all of the hydrogen atoms are substituted with a halogen atom), halogeno Examples include alkoxy groups (alkoxy groups in which some or all of the hydrogen atoms are substituted with halogen atoms). From the viewpoint of surface curability, halogen atoms, halogenoalkyl groups or halogenoalkoxy groups are preferred, and synthesis is easy. From this point of view, it is preferably unsubstituted.
  • the alkanoyl group examples include an acetyl group, a propanoyl group, and a butanoyl group. Among these, from the viewpoint of sensitivity, an acetyl group or a propanoyl group is preferable, and an acetyl group is more preferable.
  • the substituent that the alkanoyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like, and it is preferably unsubstituted from the viewpoint of sensitivity.
  • the number of carbon atoms of the aryloyl group in R 2 is not particularly limited, but is preferably 7 or more from the viewpoint of sensitivity. Further, from the viewpoint of sensitivity, it is preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less.
  • aryloyl group examples include a benzoyl group, a methylbenzoyl group, and a naphthoyl group, and among these, a benzoyl group is more preferable from the viewpoint of sensitivity.
  • R 2 is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
  • a methyl group an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group.
  • An octyl group or a 2-ethylhexyl group is preferable, and a 2-ethylhexyl group is more preferable.
  • R 3 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and a 2-ethylhexyl group. Further preferred.
  • Examples of the aromatic ring group for R 4 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number is preferably 30 or less, more preferably 12 or less, and even more preferably 8 or less. Moreover, it is 4 or more normally, and it is preferable that it is 6 or more.
  • the aromatic heterocyclic group means an aromatic heterocyclic ring having one free atomization.
  • the aromatic heterocyclic ring of the aromatic heterocyclic group may be a single ring or a condensed ring.
  • Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, an alkoxy group, and a halogen atom. From the viewpoint of solubility, an alkyl group or an alkoxy group is preferable, and an alkyl group is more preferable. A methyl group is more preferable.
  • the number of substituents is not particularly limited, but from the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Moreover, from a compatible viewpoint, 10 or less are preferable, 5 or less are more preferable, and 4 or less are more preferable.
  • R 4 is preferably an aromatic hydrocarbon ring group which may have a substituent, and is preferably an aromatic hydrocarbon ring group having two or more methyl groups. Is more preferable, and a mesityl group is more preferable.
  • R 5 and R 6 each independently represents a benzene ring or a naphthalene ring which may have a substituent. However, at least one of R 5 and R 6 is a naphthalene ring which may have a substituent. As a specific combination, R 5 is a benzene ring which may have a substituent, R 6 is a naphthalene ring which may have a substituent, and R 5 has a substituent. A combination that is an optionally substituted naphthalene ring and R 6 is a benzene ring that may have a substituent, R 5 is a naphthalene ring that may have a substituent, and R 6 has a substituent. The combination which is the naphthalene ring which may have is mentioned.
  • R 5 is a naphthalene ring which may have a substituent
  • R 6 is a benzene ring which may have a substituent
  • R 5 is an optionally substituted benzene ring
  • R 6 is bonded to the 2-position
  • X is bonded to the 4-position
  • R 6 is an optionally substituted benzene ring
  • an N atom is bonded to the 1-position of the benzene ring
  • R 5 is bonded to the 2-position
  • Z is bonded to the 4-position.
  • R 5 is an optionally substituted naphthalene ring
  • X, N atom and R 6 bonded to R 5 in the formula (I) may be bonded to any position of the naphthalene ring.
  • the N atom bonded to the 1-position of the naphthalene ring, R 6 is attached to the 2-position
  • R 6 is bonded to the 1-position of the naphthalene ring
  • the N atom at the 2-position Are bonded
  • X is bonded to the 6-position.
  • R 6 is an optionally substituted naphthalene ring
  • Z, N atom and R 5 bonded to R 6 in the formula (I) are bonded to any position of the naphthalene ring.
  • the N atom bonded to the 1-position of the naphthalene ring, R 5 is attached to the 2-position
  • aspects and that Z is attached to the 4-position R 5 is bonded to the 1-position of the naphthalene ring
  • the N atom at the 2-position Are bonded and Z is bonded to the 6-position.
  • Examples of the substituent that the benzene ring or naphthalene ring in R 5 and R 6 may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like. From the viewpoint of sensitivity, it is more preferably unsubstituted.
  • At least one of R 1 and R 4 has a —OR 7 group as a substituent.
  • R 1 may have a —OR 7 group
  • R 4 may have a —OR 7 group
  • R 1 and R 4 may each independently have a —OR 7 group. .
  • R 1 has a —OR 7 group.
  • the number of halogen atoms contained in the halogenoalkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more from the viewpoint of solubility. Moreover, it is preferable that it is 7 or less from a compatible viewpoint, It is more preferable that it is 6 or less, It is further more preferable that it is 5 or less.
  • halogenoalkyl group examples include 2,2,3,3-tetrafluoropropyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,4,4,5,5-octa
  • examples thereof include a fluoropentyl group, and among these, 2,2,3,3-tetrafluoropropyl group is more preferable from the viewpoint of ease of production.
  • substituent that the halogenoalkyl group may have include a hydroxyl group and an alkoxy group. From the viewpoint of ease of production, the substituent is preferably unsubstituted.
  • X represents a direct bond or a carbonyl group, preferably a direct bond from the viewpoint of adhesion, and preferably a carbonyl group from the viewpoint of sensitivity.
  • Z represents a direct bond or a carbonyl group, preferably a direct bond from the viewpoint of adhesion, and preferably a carbonyl group from the viewpoint of sensitivity.
  • oxime ester compound represented by the general formula (I) include the following.
  • the photopolymerization initiator (c) in the photosensitive coloring composition of the present invention contains an oxime ester compound represented by the general formula (I), but further contains another photopolymerization initiator. Also good.
  • photopolymerization initiators include, for example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A 2000-56118 Hexaarylbiimidazole derivatives described in the publication; N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in JP-A-10-39503; Radical activators such as N-aryl- ⁇ -amino acid salts and N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750 , International Publication No. 2008/077554, International Publication No. 2009/1311 Such oxime ester derivatives as described in No. 9, and the like.
  • a photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
  • a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
  • sensitizing dyes xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335
  • amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
  • Benzophenone compounds such as 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) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazol
  • polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done.
  • a polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound.
  • the ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.
  • a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly preferable to use.
  • the number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less. Yes, more preferably 7 or less. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit or less.
  • polyfunctional ethylenic monomer examples include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound.
  • esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
  • itaconic acid ester replaced by itaconate
  • ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include 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 glycerin.
  • a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted.
  • urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).
  • (meth) acrylic acid alkyl ester as (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.
  • organic solvents those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of applicability, and those having a boiling point in the range of 120 to 280 ° C. are more preferable.
  • the boiling point here means the boiling point at a pressure of 1013.25 hPa.
  • organic solvents include the following. 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, 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 ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as 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;
  • 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;
  • aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
  • 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 Linear or cyclic esters such as butyl, ⁇ -butyrolactone;
  • organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name). These organic solvents may be used alone or in combination of two or more.
  • glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
  • glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • the organic solvent used in combination glycol monoalkyl ethers are particularly preferable.
  • propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.
  • Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease.
  • the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
  • an organic solvent having a boiling point of 150 ° C. or higher hereinafter sometimes referred to as “high boiling point solvent”.
  • diethylene glycol mono-n-butyl ether diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effects.
  • the content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass.
  • the drying temperature of the composition Tends to be able to suppress slowing down and to prevent problems such as tact failure in the vacuum drying process and pre-baked pin marks
  • Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
  • a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable.
  • a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, disperses the pigment.
  • a basic functional group such as a primary, secondary or tertiary amino group
  • a quaternary ammonium base such as pyridine, pyrimidine or pyrazine
  • polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
  • examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
  • a dispersant examples include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
  • the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group. It is particularly preferable to include it.
  • a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.
  • 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.
  • Aromatic diisocyanates hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates, dimer acid diisocyanates and other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetra Aliphatic diisocyanates having an aromatic ring such as tilxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Examples thereof include triiso
  • polyisocyanate is a trimer of organic diisocyanate, and the most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
  • the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
  • an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
  • Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
  • polyether glycol examples include polyether diol, polyether ester diol, and a mixture of two or more of these.
  • polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
  • Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
  • the most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (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, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,
  • Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and 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 includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
  • the tertiary amino group is not particularly limited, and examples thereof include 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 an 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 and the like.
  • the preferred blending ratio of the raw materials for producing the urethane polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound.
  • the production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin.
  • a solvent for production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of
  • the weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor.
  • Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid.
  • Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.
  • the B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. These may be contained in the B block in any form of random copolymerization or block copolymerization.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
  • the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method.
  • the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
  • the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer.
  • the / B block ratio is preferably 1/99 to 80/20, and particularly preferably 5/95 to 60/40 (mass ratio), and within this range, a balance between dispersibility and storage stability can be ensured.
  • the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. There exists a tendency which can ensure favorable dispersibility by making it in the range.
  • the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
  • the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating” It is preferable to have a unit (i) ”.
  • R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 34 is a hydrogen atom or a methyl group.
  • X is a divalent linking group
  • Y ⁇ is a counter anion.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 1 or more and preferably 10 or less. The following is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the carbon number of the aralkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less. The following is more preferable.
  • the aralkyl group examples include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
  • R 31 to R 33 are preferably each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group or an ethyl group. It is preferable that R 32 is a phenylmethylene group or a phenylethylene group, R 31 and R 33 are methyl groups, and R 32 is a phenylmethylene group.
  • the polymer dispersant when it has a tertiary amine as a functional group, from the viewpoint of dispersibility, it may be a repeating unit represented by the following formula (ii) (hereinafter referred to as “repeating unit (ii)”). .).
  • R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 35 and R 36 may be bonded to each other to form a cyclic structure.
  • R 37 is a hydrogen atom or a methyl group.
  • Z is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 of the above formula (ii) those exemplified as R 31 to R 33 of the above formula (i) may be preferably employed. it can.
  • aryl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) should be preferably employed.
  • aralkyl group optionally having a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) may be preferably employed. it can.
  • R 35 and R 36 are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
  • alkyl group, aralkyl group or aryl group in R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, etc. are mentioned.
  • examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, —COOR 44 — group (wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), etc. Is a —COO—R 44 — group.
  • examples of Y ⁇ of the counter anion include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , PF 6 ⁇ and the like.
  • the content ratio of the repeating unit represented by the formula (i) is not particularly limited. From the viewpoint of dispersibility, it is preferably 60 mol% or less based on the total content of the repeating units represented by the formula (i) and the repeating units represented by the formula (ii). Preferably it is 50 mol% or less, More preferably, it is 40 mol% or less, Most preferably, it is 35 mol% or less. Further, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
  • the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, and 5 mol. % Or more is more preferable, and it is further more preferable that it is 10 mol% or more. Moreover, it is preferable that it is 50 mol% or less, It is more preferable that it is 30 mol% or less, It is further more preferable that it is 20 mol% or less, It is especially preferable that it is 15 mol% or less.
  • the content ratio of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more from the viewpoint of dispersibility. % Or more, more preferably 15 mol% or more, and particularly preferably 20 mol% or more. Further, it is preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less.
  • the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii)” from the viewpoint of improving compatibility with binder components such as a solvent and improving dispersion stability. It is preferable that it has.
  • R 40 is an ethylene group or a propylene group
  • R 41 is an alkyl group which may have a substituent
  • R 42 is a hydrogen atom or a methyl group.
  • n is an integer of 1 to 20.
  • the number of carbon atoms of the alkyl group which may have a substituent in R 41 of the above formula (iii) is not particularly limited, but is usually 1 or more and preferably 2 or more. Moreover, it is preferable that it is 10 or less, and it is more preferable that it is 6 or less.
  • alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
  • a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is more preferable.
  • it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • n is preferably 1 or more, and more preferably 2 or more, from the viewpoints of compatibility and dispersibility with respect to a binder component such as a solvent. Moreover, it is preferable that it is 10 or less, and it is more preferable that it is 5 or less.
  • the content ratio of the repeating unit represented by the formula (iii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. More preferably, it is more preferably 4 mol% or more. Moreover, it is preferable that it is 30 mol% or less, It is more preferable that it is 20 mol% or less, It is further more preferable that it is 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent tends to be compatible with dispersion stability.
  • the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv)” from the viewpoint of improving the compatibility of the dispersing agent with a binder component such as a solvent and improving dispersion stability. ) ").).
  • R 38 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 39 is a hydrogen atom or a methyl group.
  • the number of carbon atoms of the aryl group which may have a substituent is not particularly limited, it is usually 6 or more. Further, it is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less.
  • the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
  • a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
  • the carbon number of the aralkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less.
  • the aralkyl group examples include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group.
  • a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
  • R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group from the viewpoints of solvent compatibility and dispersion stability.
  • the content of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is more preferably 50 mol% or more. Moreover, it is preferable that it is 80 mol% or less, and it is more preferable that it is 70 mol% or less.
  • the polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv).
  • repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.
  • the polymer dispersant is composed of an A block having the repeating unit (i) and the repeating unit (ii), and a B block not having the repeating unit (i) and the repeating unit (ii). It is preferable that it is a block copolymer which has these.
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
  • the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).
  • a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block.
  • Examples of such a repeating unit include the aforementioned (meth) acrylic acid ester-based unit.
  • Examples include a repeating unit derived from a monomer.
  • the content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
  • the content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
  • the dispersant is preferably used in combination with a pigment derivative described later.
  • the photosensitive coloring composition of the present invention includes an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative. Etc. can be suitably blended.
  • an adhesion improver such as a silane coupling agent, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative. Etc. can be suitably blended.
  • the photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
  • an adhesion improver a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
  • the type of silane coupling agent various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.
  • Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.
  • Pigment derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
  • a pigment derivative as a dispersion aid
  • As pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
  • derivatives such as phthalocyanines and quinophthalones are preferable.
  • Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
  • R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms
  • R 61 represents R 62, R 63 , R 64 , R 65 , one of R 66 and R 67
  • R 61 represents R 62, R 63, one of R 64 and R 65 are -CH 2 oR 68 group in the case of an aryl group having 6 to 12 carbon atoms
  • R 62 , R 63 , R 64 , R 65 , R 66 and R 67 independently of one another, represent hydrogen or a —CH 2 OR 68 group, wherein R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Melamine compounds corresponding to the general formula (6) that is, compounds of the following general formula (6-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.
  • guanamine compounds corresponding to the general formula (6) that is, compounds in which R 61 in the general formula (6) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.
  • crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount of the crosslinking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.
  • Mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol (3-mercaptobutyrate), butanediol bis (3-mercapto
  • the content of (a) the colorant is usually 10% by mass or more and preferably 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. Furthermore, it is preferable that it is 30 mass% or more. Moreover, it is preferable normally that it is 60 mass% or less, and it is further preferable that it is 50 mass% or less.
  • At least one pigment selected from the group consisting of a blue pigment and a violet pigment with respect to 100 parts by mass of (a) the colorant is 20 parts by mass or more, More preferably, it is 30 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and 65 parts by mass or more. Most preferably it is. Also, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less. There exists a tendency which can ensure light-shielding property by setting it as the said lower limit or more, and there exists a tendency which can ensure plate-making characteristic by setting it as the said upper limit or less.
  • the amount of at least one pigment selected from the group consisting of a red pigment and an orange pigment is preferably 0 parts by mass or more, with respect to 100 parts by mass of the colorant. More preferably, it is more preferably 2 parts by mass or more. Further, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and 0 part by mass. Most preferred. There exists a tendency for sufficient optical density (OD) to be acquired by setting it as the said lower limit or more, and there exists a tendency which can ensure platemaking characteristics by setting it as the said upper limit or less.
  • OD optical density
  • At least one pigment selected from the group consisting of a blue pigment and a violet pigment is preferably 20 parts by mass or more and 100 parts by mass or more with respect to 100 parts by mass of the colorant. More preferably, it is more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 65 parts by mass or more. . Moreover, it is preferable that it is 90 mass parts or less, It is more preferable that it is 85 mass parts or less, It is further more preferable that it is 80 mass parts or less. There exists a tendency which can ensure light-shielding property by setting it as the said lower limit or more, and there exists a tendency which can ensure plate-making characteristic by setting it as the said upper limit or less.
  • the content of the alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably, based on the total solid content of the photosensitive coloring composition of the present invention. Is 25% by mass or more, particularly preferably 30% by mass or more. Usually, it is 85 mass% or less, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 40 mass% or less.
  • the content rate of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more. More preferably, it is 2% by mass or more, still more preferably 3% by mass or more, and particularly preferably 4% by mass or more. Usually, it is 15 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 7 mass% or less.
  • the content of the oxime ester compound represented by the general formula (I) contained in the photopolymerization initiator is not particularly limited, but is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50 mass% or more, more preferably 70 mass% or more, particularly preferably 90 mass% or more, and usually 100 mass% or less. By setting it as the said lower limit or more, there exists a tendency for the surface smoothness of the hardened
  • the content ratio of the polymerization accelerator is preferably 0.05% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention. 10% by mass or less, preferably 5% by mass or less.
  • the polymerization accelerator is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (c). It is preferable to use in proportion.
  • the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.
  • the content ratio of the ethylenically unsaturated compound is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, based on the total solid content of the photosensitive coloring composition of the present invention.
  • (D) By making the content rate of an ethylenically unsaturated compound below the said upper limit, it becomes the tendency which suppresses that the permeability of the developing solution to an exposure part becomes high, and obtains a favorable image easily. is there.
  • the lower limit of the content rate of (d) ethylenically unsaturated compound is 1 mass% or more normally, Preferably it is 5 mass% or more.
  • the photosensitive coloring composition of the present invention has a solid content concentration of usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30 by using the solvent (e). It is prepared so that it may become below mass%.
  • the content of the dispersant is usually 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more in the solid content of the photosensitive coloring composition. Moreover, 30 mass% or less and 20 mass% or less are preferable normally, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the content ratio of the (f) dispersant to (a) 100 parts by mass of the colorant is usually preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less. It is preferable that it is 30 mass parts or less.
  • the content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4%, based on the total solid content in the photosensitive coloring composition. ⁇ 2% by weight.
  • the effect of improving the adhesion can be sufficiently obtained by setting the content ratio of the adhesion improver to the above lower limit value or more, and the sensitivity is lowered by setting it to the upper limit value or less, or a residue remains after development. There exists a tendency which can suppress becoming a defect.
  • the content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0% with respect to the total solid content in the photosensitive coloring composition. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass.
  • the photosensitive coloring composition of the present invention can be suitably used for forming a colored spacer, and is preferably black from the viewpoint of being used as a colored spacer.
  • the optical density (OD) per 1 ⁇ m of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more. .8 or more is particularly preferable. Usually, it is 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less.
  • the dispersion treatment is usually preferably carried out in a system in which a part or all of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) an alkali-soluble resin are used together (hereinafter referred to as dispersion).
  • the mixture subjected to the treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”).
  • a polymer dispersant as the dispersant (f) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
  • a pigment dispersion containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
  • a colorant e) organic solvent, and (f) dispersant that can be used in the pigment dispersion
  • those described as those that can be used in the photosensitive coloring composition are preferably employed. Can do.
  • a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
  • the dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.
  • the standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300.
  • the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like.
  • the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
  • the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
  • the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution.
  • fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
  • a cured product can be obtained by curing the photosensitive coloring composition of the present invention.
  • a cured product obtained by curing the photosensitive coloring composition can be suitably used as a colored spacer.
  • the material thereof is not particularly limited.
  • Transparent substrates are mainly used.
  • materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets made of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy.
  • thermosetting resin sheets such as resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses.
  • a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
  • the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness.
  • the thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • the photosensitive coloring composition of the present invention is used in the same applications as known photosensitive coloring compositions for color filters.
  • a colored spacer black photo spacer
  • the case where it is used as a colored spacer will be described according to a specific example of a method for forming a black photo spacer using the photosensitive colored composition of the present invention.
  • a photosensitive coloring composition is supplied in a film shape or a pattern shape by a method such as coating on a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermosetting treatment as necessary.
  • the photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent.
  • a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method.
  • the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.
  • the coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, particularly preferably 1 ⁇ m to 7 ⁇ m.
  • the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.
  • the final height of the black photo spacers is different.
  • a known substrate such as a glass substrate can be used as the substrate.
  • the substrate surface is preferably a flat surface.
  • Drying method Drying after supplying the photosensitive coloring composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.
  • Drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used.
  • the drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used.
  • the temperature is selected in the range of 30 seconds to 3 minutes.
  • Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating with an ultraviolet light source or a visible light source through this mask pattern.
  • the exposure mask is placed close to the coating film of the photosensitive coloring composition, or the exposure mask is arranged at a position away from the coating film of the photosensitive coloring composition.
  • a method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used.
  • the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.
  • a light shielding portion (light transmittance 0%) and a plurality of openings have the highest average light transmittance.
  • An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a high opening (complete transmission opening) is used.
  • a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known. Also known is a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.
  • the light source used for the above exposure is not particularly limited.
  • the light source for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser,
  • laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser.
  • An optical filter can also be used when irradiating light of a specific wavelength.
  • the optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
  • a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
  • Energy of exposure generally, 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or less.
  • the distance between the exposure object and the mask pattern is usually 10 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more.
  • it is 500 micrometers or less normally, Preferably it is 400 micrometers or less, More preferably, it is 300 micrometers or less.
  • an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
  • This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
  • Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, 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.
  • Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
  • surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters
  • Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfon
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
  • the organic solvent can be used alone or in combination with an aqueous solution.
  • the development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C.
  • the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
  • thermosetting treatment If necessary, the substrate after development may be subjected to additional exposure by the same method as the exposure method described above, or may be subjected to thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.
  • the size and shape of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which the colored spacer is applied, but the photosensitive colored composition of the present invention is particularly suitable for the height of the spacer and the sub-spacer by photolithography. It is useful for simultaneously forming different black photo spacers, in which case the height of the spacer is usually about 2 to 7 ⁇ m, and the sub-spacer is usually about 0.2 to 1.5 ⁇ m lower than the spacer.
  • the optical density (OD) per 1 ⁇ m of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, and further preferably 1.8 or more from the viewpoint of light shielding properties. Moreover, it is 4.0 or less normally, and it is preferable that it is 3.0 or less.
  • the optical density (OD) is a value measured by a method described later.
  • the color filter of the present invention is provided with the colored spacer of the present invention as described above.
  • a black matrix, a red, green, and blue pixel coloring layer, and an overcoat layer are stacked to form a colored spacer, and then an alignment film is formed.
  • the liquid crystal provided with the colored spacer of the present invention is formed by bonding the color filter having the colored spacer of the present invention and the liquid crystal driving side substrate to form a liquid crystal cell, and injecting the liquid crystal into the formed liquid crystal cell.
  • An image display device such as a display device can be manufactured.
  • the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
  • THPA tetrahydrophthalic anhydride
  • the weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, and the acid value was 80 mgKOH / g.
  • Polymer.Amine value is 70 mgKOH / g.
  • Acid value is 1 mgKOH / g or less.
  • the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).
  • the content of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.
  • DPHA Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
  • KAYAMER PM-21 phosphate containing methacryloyl group
  • optical density (OD) was measured with a transmission densitometer (“D200-II” manufactured by Gretag Macbeth). Furthermore, the film thickness at the measurement location was also measured, and the optical density (unit OD) per unit film thickness (1 ⁇ m) was calculated.
  • the surface roughness Sa (arithmetic mean roughness) in a 70 ⁇ m ⁇ 70 ⁇ m field of view using a 50 ⁇ optical lens with a 3D non-contact surface shape measurement system Micromap of Ryoka System Co., Ltd. Nm).
  • ⁇ Preparation of pigment dispersion 1> The pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was obtained. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mm ⁇ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the pigment dispersion 1 was prepared by separating the beads and the dispersion with a filter.
  • Pigment dispersion 2 similar to pigment dispersion 1 except that the pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so as to have the mass ratio described in Table 1. And 3 were prepared.
  • Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small amount of Na, Ca, and S was used, and a coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry.
  • the slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Mitsubishi Chemical Corporation) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
  • Examples 1 and 2 Comparative Examples 1 to 3
  • each component was added so that the blending ratio shown in Table 2 was added, and PGMEA was further added so that the solid content was 22% by mass.
  • a colored composition was prepared.
  • the value of the upper stage in Table 2 has shown the usage-amount of each component.
  • the value of the lower stage has shown the solid content of each component by the content rate with respect to the total solid content of the photosensitive coloring composition.
  • a completely transmissive opening of a circular pattern of various diameters of 5 to 50 ⁇ m (5 to 20 ⁇ m: every 1 ⁇ m, 25 ⁇ m to 50 ⁇ m: every 5 ⁇ m) and a diameter of 5 to 50 ⁇ m (every 5 to 20 ⁇ m: every 1 ⁇ m) , 25 ⁇ m to 50 ⁇ m: every 5 ⁇ m) exposure processing was performed using an exposure mask having an intermediate transmission opening having a circular pattern with various diameters and a linear opening (complete transmission) having a width of 100 ⁇ m.
  • the intermediate transmission opening is a Cr oxide thin film having a light transmittance of 10 ⁇ 2% at a wavelength of 365 nm.
  • the exposure gap (distance between the mask and the coated surface) was 220 ⁇ m.
  • ultraviolet rays having an intensity of 32 mW / cm 2 at a wavelength of 365 nm were used, and the exposure amount was 100 mJ / cm 2 .
  • ultraviolet irradiation was performed under air.
  • a developer comprising an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant (“A-60” manufactured by Kao Corporation) was used, and the water pressure was 0 at 25 ° C.
  • A-60 a nonionic surfactant manufactured by Kao Corporation
  • the shower development time was adjusted between 10 and 120 seconds, and was 1.5 times as long as the unexposed coating film was dissolved and removed. By these operations, a pattern from which unnecessary portions were removed was obtained.
  • substrate with which the said pattern was formed was heated at 230 degreeC for 20 minute (s) in oven, the pattern was hardened, and the substantially cylindrical spacer pattern was obtained.

Abstract

La présente invention vise à fournir une composition colorante photosensible utilisée de préférence pour former en particulier un espaceur coloré et apte à former un motif ayant de bonnes propriétés de blocage de lumière et un excellent lissé de surface. La composition colorante photosensible servant à former l'espaceur coloré, selon la présente invention, contient a) un colorant, b) une résine soluble dans l'alcali, (c) un initiateur de photopolymérisation, (d) un composé à insaturation éthylénique, (e) un solvant, et f) un dispersant. L'initiateur de photopolymérisation contient un composé ester d'oxime représenté par la formule (I).
PCT/JP2016/057678 2015-03-11 2016-03-10 Composition colorante photosensible pour former un espaceur coloré, produit durci, espaceur coloré, et dispositif d'affichage d'image WO2016143878A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020177025400A KR102491215B1 (ko) 2015-03-11 2016-03-10 착색 스페이서 형성용 감광성 착색 조성물, 경화물, 착색 스페이서, 화상 표시 장치
CN201680014325.2A CN107407881A (zh) 2015-03-11 2016-03-10 着色间隔物形成用感光性着色组合物、固化物、着色间隔物、图像显示装置
JP2017505412A JP7131907B2 (ja) 2015-03-11 2016-03-10 感光性着色組成物、硬化物、着色スペーサー、画像表示装置

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015048577 2015-03-11
JP2015-048577 2015-03-11
JP2015-048578 2015-03-11
JP2015048578 2015-03-11
JP2015157456 2015-08-07
JP2015-157456 2015-08-07

Publications (1)

Publication Number Publication Date
WO2016143878A1 true WO2016143878A1 (fr) 2016-09-15

Family

ID=56879478

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/057678 WO2016143878A1 (fr) 2015-03-11 2016-03-10 Composition colorante photosensible pour former un espaceur coloré, produit durci, espaceur coloré, et dispositif d'affichage d'image

Country Status (5)

Country Link
JP (2) JP7131907B2 (fr)
KR (1) KR102491215B1 (fr)
CN (2) CN107407881A (fr)
TW (2) TWI776205B (fr)
WO (1) WO2016143878A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017038708A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Composition photosensible de coloration, film durci, filtre de couleur, film de protection contre la lumière, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, et procédé de fabrication de film durci
JPWO2016158114A1 (ja) * 2015-03-30 2018-01-18 富士フイルム株式会社 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP6374595B1 (ja) * 2017-09-26 2018-08-15 東京応化工業株式会社 感光性樹脂組成物、硬化膜、表示装置、及びパターン形成方法
WO2018151079A1 (fr) * 2017-02-15 2018-08-23 三菱ケミカル株式会社 Composition de coloration photosensible, produit durci, élément d'espacement coloré et dispositif d'affichage d'image
JP2018141968A (ja) * 2017-02-24 2018-09-13 新日鉄住金化学株式会社 遮光膜用の感光性樹脂組成物、遮光膜、液晶表示装置、スペーサー機能を有する遮光膜の製造方法、および液晶表示装置の製造方法
CN108693707A (zh) * 2017-03-29 2018-10-23 东友精细化工有限公司 黑色感光性树脂组合物及利用其制造的显示装置
JP2018205605A (ja) * 2017-06-07 2018-12-27 三菱ケミカル株式会社 着色感光性樹脂組成物、硬化物、有機電界発光素子、画像表示装置及び照明
JP2019023671A (ja) * 2017-07-21 2019-02-14 東京応化工業株式会社 感光性組成物、パターン形成方法、硬化物、及び表示装置
KR101923832B1 (ko) * 2017-11-20 2019-02-27 동우 화인켐 주식회사 착색 감광성 수지 조성물 및 이로부터 형성되는 패턴층, 이를 포함하는 컬러필터 및 이를 포함하는 액정 디스플레이 장치
JP2019045659A (ja) * 2017-08-31 2019-03-22 東京応化工業株式会社 感光性組成物、硬化物形成方法、硬化物、画像表示装置用パネル、及び画像表示装置
CN109923475A (zh) * 2016-10-14 2019-06-21 三菱化学株式会社 感光性着色组合物、固化物、着色间隔物、图像显示装置
JP2019120768A (ja) * 2017-12-28 2019-07-22 東京応化工業株式会社 感光性組成物、硬化物、硬化物形成方法、カラーフィルター、及び画像表示装置
CN111596522A (zh) * 2019-02-21 2020-08-28 阪田油墨株式会社 着色组合物以及含有其的着色抗蚀剂组合物
JP2021006842A (ja) * 2019-06-27 2021-01-21 東京応化工業株式会社 感光性組成物、硬化物、ブラックマトリクス、ブラックバンク、カラーフィルター、画像表示装置、及びパターン化された硬化膜の製造方法
JP7439530B2 (ja) 2020-01-23 2024-02-28 Ｔｏｐｐａｎホールディングス株式会社 光モジュール及び表示装置

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102080235B1 (ko) * 2016-10-28 2020-02-21 삼성에스디아이 주식회사 감광성 수지 조성물, 이를 이용한 흑색 감광성 수지막 및 컬러필터
JP7351221B2 (ja) * 2017-06-30 2023-09-27 三菱ケミカル株式会社 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
KR102509789B1 (ko) 2018-03-29 2023-03-20 동우 화인켐 주식회사 착색 감광성 수지 조성물, 컬러 필터 및 이를 구비한 화상 표시 장치
TW202116409A (zh) * 2019-09-06 2021-05-01 日商三菱化學股份有限公司 感光性著色組合物、硬化物、影像顯示裝置、及影像顯示裝置用之顏料分散液
KR20220095288A (ko) 2020-12-29 2022-07-07 삼성디스플레이 주식회사 표시 장치 및 이를 포함하는 타일형 표시 장치
CN113372757A (zh) * 2021-07-29 2021-09-10 业成科技（成都）有限公司 紫外光固化油墨

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006162784A (ja) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd 感光性着色組成物、及びそれを用いたカラーフィルタ
WO2011152066A1 (fr) * 2010-06-04 2011-12-08 ダイトーケミックス株式会社 Composé ester d'oxime, procédé de production d'un composé ester d'oxime, amorceur de photopolymérisation et composition photosensible
JP2013147483A (ja) * 2012-01-20 2013-08-01 Hunet Plus Co Ltd 新規な高感度アルファケトオキシムエステル光重合開始剤及びこの化合物を含む光重合組成物
JP2014009325A (ja) * 2012-07-02 2014-01-20 Nippon Kagaku Kogyosho:Kk 新規な光重合開始剤及びこれらを用いた感光性樹脂組成物
WO2014103628A1 (fr) * 2012-12-27 2014-07-03 富士フイルム株式会社 Composition pour filtre coloré, filtre d'émission infrarouge et procédé de fabrication de filtre d'émission infrarouge et capteur infrarouge
JP2014139668A (ja) * 2012-12-20 2014-07-31 Mitsubishi Chemicals Corp 着色硬化物体及びその製造方法と、カラーフィルター、及び液晶表示装置

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08234212A (ja) 1995-02-28 1996-09-13 Casio Comput Co Ltd 液晶表示素子
JP2006162874A (ja) * 2004-12-06 2006-06-22 Fujikura Ltd コネクタ付き光ファイバケーブル
KR101266295B1 (ko) 2009-09-09 2013-05-23 제일모직주식회사 흑색 감광성 수지 조성물 및 이를 이용하여 형성된 차광층
KR101831912B1 (ko) 2010-10-05 2018-02-26 바스프 에스이 벤조카르바졸 화합물의 옥심 에스테르 유도체 및 광중합성 조성물에서의 광개시제로서의 그의 용도
JP2012181509A (ja) * 2011-02-08 2012-09-20 Mitsubishi Chemicals Corp 着色感光性組成物、着色スペーサ、カラーフィルター、及び液晶表示装置
KR101349622B1 (ko) * 2011-08-26 2014-01-10 롬엔드하스전자재료코리아유한회사 광중합성 불포화 수지, 이를 포함하는 감광성 수지 조성물 및 이로부터 형성되는 차광성 스페이서와 액정 디스플레이 장치
WO2013062011A1 (fr) * 2011-10-25 2013-05-02 三菱化学株式会社 Composition de résine photosensible colorée, espaceur coloré, filtre coloré et dispositif d'affichage à cristaux liquides
KR102006041B1 (ko) * 2011-12-07 2019-07-31 바스프 에스이 옥심 에스테르 광개시제
KR102078989B1 (ko) 2012-01-31 2020-02-19 미쯔비시 케미컬 주식회사 착색 감광성 조성물, 블랙 포토 스페이서 및 컬러 필터
US9217070B2 (en) 2012-06-01 2015-12-22 Basf Se Black colorant mixture
JP6031901B2 (ja) * 2012-09-06 2016-11-24 東洋インキＳｃホールディングス株式会社 感光性着色組成物、着色膜及びカラーフィルタ
KR101658374B1 (ko) * 2013-01-25 2016-09-22 롬엔드하스전자재료코리아유한회사 컬럼 스페이서 및 블랙 매트릭스를 동시에 구현할 수 있는 착색 감광성 수지 조성물
JP6096146B2 (ja) * 2013-05-10 2017-03-15 富士フイルム株式会社 着色組成物、着色硬化膜、カラーフィルタ、固体撮像素子および画像表示装置
WO2014208348A1 (fr) * 2013-06-24 2014-12-31 東レ株式会社 Composition de résine noire pour écrans tactiles
KR101966125B1 (ko) * 2014-05-01 2019-04-05 후지필름 가부시키가이샤 착색 조성물, 막, 컬러 필터, 패턴 형성 방법, 컬러 필터의 제조 방법, 고체 촬상 소자 및 적외선 센서

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006162784A (ja) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd 感光性着色組成物、及びそれを用いたカラーフィルタ
WO2011152066A1 (fr) * 2010-06-04 2011-12-08 ダイトーケミックス株式会社 Composé ester d'oxime, procédé de production d'un composé ester d'oxime, amorceur de photopolymérisation et composition photosensible
JP2013147483A (ja) * 2012-01-20 2013-08-01 Hunet Plus Co Ltd 新規な高感度アルファケトオキシムエステル光重合開始剤及びこの化合物を含む光重合組成物
JP2014009325A (ja) * 2012-07-02 2014-01-20 Nippon Kagaku Kogyosho:Kk 新規な光重合開始剤及びこれらを用いた感光性樹脂組成物
JP2014139668A (ja) * 2012-12-20 2014-07-31 Mitsubishi Chemicals Corp 着色硬化物体及びその製造方法と、カラーフィルター、及び液晶表示装置
WO2014103628A1 (fr) * 2012-12-27 2014-07-03 富士フイルム株式会社 Composition pour filtre coloré, filtre d'émission infrarouge et procédé de fabrication de filtre d'émission infrarouge et capteur infrarouge

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016158114A1 (ja) * 2015-03-30 2018-01-18 富士フイルム株式会社 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP2018173660A (ja) * 2015-03-30 2018-11-08 富士フイルム株式会社 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP7232881B2 (ja) 2015-03-30 2023-03-03 富士フイルム株式会社 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP2022023920A (ja) * 2015-03-30 2022-02-08 富士フイルム株式会社 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JPWO2017038708A1 (ja) * 2015-08-31 2018-02-22 富士フイルム株式会社 着色感光性組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像素子、画像表示装置、および、硬化膜の製造方法
WO2017038708A1 (fr) * 2015-08-31 2017-03-09 富士フイルム株式会社 Composition photosensible de coloration, film durci, filtre de couleur, film de protection contre la lumière, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, et procédé de fabrication de film durci
CN109923475A (zh) * 2016-10-14 2019-06-21 三菱化学株式会社 感光性着色组合物、固化物、着色间隔物、图像显示装置
CN109923475B (zh) * 2016-10-14 2022-12-02 三菱化学株式会社 感光性着色组合物、固化物、着色间隔物、图像显示装置
WO2018151079A1 (fr) * 2017-02-15 2018-08-23 三菱ケミカル株式会社 Composition de coloration photosensible, produit durci, élément d'espacement coloré et dispositif d'affichage d'image
JP6380723B1 (ja) * 2017-02-15 2018-08-29 三菱ケミカル株式会社 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP7396786B2 (ja) 2017-02-24 2023-12-12 日鉄ケミカル＆マテリアル株式会社 遮光膜用の感光性樹脂組成物、遮光膜、液晶表示装置、スペーサー機能を有する遮光膜の製造方法、および液晶表示装置の製造方法
JP2018141968A (ja) * 2017-02-24 2018-09-13 新日鉄住金化学株式会社 遮光膜用の感光性樹脂組成物、遮光膜、液晶表示装置、スペーサー機能を有する遮光膜の製造方法、および液晶表示装置の製造方法
CN108693707A (zh) * 2017-03-29 2018-10-23 东友精细化工有限公司 黑色感光性树脂组合物及利用其制造的显示装置
JP2022109931A (ja) * 2017-03-29 2022-07-28 東友ファインケム株式会社 黒色感光性樹脂組成物、これを利用して製造された表示装置
JP2018205605A (ja) * 2017-06-07 2018-12-27 三菱ケミカル株式会社 着色感光性樹脂組成物、硬化物、有機電界発光素子、画像表示装置及び照明
JP7051321B2 (ja) 2017-07-21 2022-04-11 東京応化工業株式会社 感光性組成物、パターン形成方法、硬化物、及び表示装置
JP2019023671A (ja) * 2017-07-21 2019-02-14 東京応化工業株式会社 感光性組成物、パターン形成方法、硬化物、及び表示装置
JP7079581B2 (ja) 2017-08-31 2022-06-02 東京応化工業株式会社 感光性組成物、硬化物形成方法、硬化物、画像表示装置用パネル、及び画像表示装置
JP2019045659A (ja) * 2017-08-31 2019-03-22 東京応化工業株式会社 感光性組成物、硬化物形成方法、硬化物、画像表示装置用パネル、及び画像表示装置
JP2019061216A (ja) * 2017-09-26 2019-04-18 東京応化工業株式会社 感光性樹脂組成物、硬化膜、表示装置、及びパターン形成方法
JP6374595B1 (ja) * 2017-09-26 2018-08-15 東京応化工業株式会社 感光性樹脂組成物、硬化膜、表示装置、及びパターン形成方法
KR101923832B1 (ko) * 2017-11-20 2019-02-27 동우 화인켐 주식회사 착색 감광성 수지 조성물 및 이로부터 형성되는 패턴층, 이를 포함하는 컬러필터 및 이를 포함하는 액정 디스플레이 장치
JP7095989B2 (ja) 2017-12-28 2022-07-05 東京応化工業株式会社 感光性組成物、硬化物、硬化物形成方法、カラーフィルター、及び画像表示装置
JP2019120768A (ja) * 2017-12-28 2019-07-22 東京応化工業株式会社 感光性組成物、硬化物、硬化物形成方法、カラーフィルター、及び画像表示装置
CN111596522A (zh) * 2019-02-21 2020-08-28 阪田油墨株式会社 着色组合物以及含有其的着色抗蚀剂组合物
JP2021006842A (ja) * 2019-06-27 2021-01-21 東京応化工業株式会社 感光性組成物、硬化物、ブラックマトリクス、ブラックバンク、カラーフィルター、画像表示装置、及びパターン化された硬化膜の製造方法
JP7263153B2 (ja) 2019-06-27 2023-04-24 東京応化工業株式会社 感光性組成物、硬化物、ブラックマトリクス、ブラックバンク、カラーフィルター、画像表示装置、及びパターン化された硬化膜の製造方法
JP7439530B2 (ja) 2020-01-23 2024-02-28 Ｔｏｐｐａｎホールディングス株式会社 光モジュール及び表示装置

Also Published As

Publication number Publication date
KR20170126912A (ko) 2017-11-20
CN107407881A (zh) 2017-11-28
CN113608408A (zh) 2021-11-05
TWI776205B (zh) 2022-09-01
JP7131907B2 (ja) 2022-09-06
TW201634591A (zh) 2016-10-01
JP7268700B2 (ja) 2023-05-08
KR102491215B1 (ko) 2023-01-20
JPWO2016143878A1 (ja) 2017-12-28
JP2023106388A (ja) 2023-08-01
TWI763625B (zh) 2022-05-11
JP2021182150A (ja) 2021-11-25
TW202100665A (zh) 2021-01-01

Similar Documents

Publication Publication Date Title
JP7268700B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP6268508B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP6380723B1 (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP7184518B2 (ja) 着色スペーサー形成用感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP6543968B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP2016177190A (ja) 着色スペーサー形成用感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP6528475B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP2022078139A (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP6561533B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP2018205605A (ja) 着色感光性樹脂組成物、硬化物、有機電界発光素子、画像表示装置及び照明
JP2017053942A (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP7485147B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、画像表示装置
JP2019015966A (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP7230559B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
JP7006358B2 (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置
TW202035467A (zh) 感光性著色組合物、硬化物、著色間隔物、及圖像顯示裝置
JPWO2019004427A1 (ja) 感光性着色組成物、硬化物、着色スペーサー、及び画像表示装置

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: 16761844

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017505412

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20177025400

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16761844

Country of ref document: EP

Kind code of ref document: A1