WO2013062011A1 - Colored photosensitive resin composition, colored spacer, color filter, and liquid crystal display device - Google Patents

Colored photosensitive resin composition, colored spacer, color filter, and liquid crystal display device Download PDF

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Publication number
WO2013062011A1
WO2013062011A1 PCT/JP2012/077503 JP2012077503W WO2013062011A1 WO 2013062011 A1 WO2013062011 A1 WO 2013062011A1 JP 2012077503 W JP2012077503 W JP 2012077503W WO 2013062011 A1 WO2013062011 A1 WO 2013062011A1
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Prior art keywords
photosensitive composition
group
colored photosensitive
colored
alkali
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PCT/JP2012/077503
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French (fr)
Japanese (ja)
Inventor
麗華 裴
良尚 沢井
福井　誠
Original Assignee
三菱化学株式会社
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Application filed by 三菱化学株式会社 filed Critical 三菱化学株式会社
Priority to KR1020187033158A priority Critical patent/KR102007133B1/en
Priority to JP2013540808A priority patent/JP6143298B2/en
Priority to CN201280052634.0A priority patent/CN103890660B/en
Priority to KR1020147010655A priority patent/KR101921369B1/en
Publication of WO2013062011A1 publication Critical patent/WO2013062011A1/en

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    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

  • the present invention relates to a colored photosensitive composition and the like. More specifically, the present invention relates to a colored photosensitive composition that is preferably used as a colored spacer in a color filter such as a liquid crystal display, and a colored spacer, a color filter, and a liquid crystal display device formed thereby.
  • a color filter such as a liquid crystal display
  • 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 forming an LCD cell is often formed using a photosensitive composition typified by photolithography.
  • the range of application of the photosensitive composition tends to further expand in the future because it is easy to form a fine structure and it is easy to process a substrate for a large screen.
  • Patent Document 1 describes that a spacer is made light-shielding.
  • Patent Document 2 discloses that the spacer shape and level difference having different desired heights can be realized by controlling the exposure amount and the remaining film ratio.
  • Patent Document 2 relates to a spacer to which no pigment is added, and when applied to the batch formation of colored spacers to which a pigment is added, the pigment absorbs light in the ultraviolet region contributing to photopolymerization, and thus the light transmittance of the opening. It has been found that a pattern having a small number has poor curability, and it is difficult to achieve characteristics such as spacer shapes having different heights, step control, and adhesion to a substrate.
  • the present invention has been made in view of such circumstances. That is, the main problem of the present invention is that in the method for forming colored spacers having different heights by photolithography, the liquid crystal voltage holding ratio is ensured, the formation of a desired shape, the control of the step, the substrate and An object of the present invention is to provide a colored photosensitive composition having excellent adhesion. Another object of the present invention is to provide a colored spacer formed from such a colored photosensitive composition.
  • Still another object of the present invention is to provide a color filter having such a colored spacer. Still another object of the present invention is to provide a liquid crystal display device having such a color filter. Still another object of the present invention is to provide a method for collectively forming colored spacers having different heights using such a colored photosensitive composition by a photolithography method.
  • the present inventors use a specific alkali-soluble resin and a dispersant, and specify the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and the content ratio of the specific alkali-soluble resin.
  • the gist of the present invention is as follows. [1] Photolithography containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.
  • a colored photosensitive composition used to collectively form colored spacers having different heights by a method (B) the alkali-soluble resin includes at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2); (F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included, (D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7, A colored photosensitive composition in which the total proportion of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition is 12% by weight or more.
  • the total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition [2] is 20% by weight or more.
  • [3] The colored photosensitive composition according to the above [1] or [2], wherein the content ratio of (a) the colorant is less than 30% by weight with respect to the total solid content in the colored photosensitive composition.
  • AB block comprising, as a dispersant, an A block having at least one of a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group
  • an AB block copolymer comprising an A block having a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group, and The colored photosensitive composition according to any one of the above [1] to [6], comprising at least one of BAB block copolymers.
  • an AB block consisting of an A block having an amino group without a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base and an amino group.
  • a color filter comprising the colored spacer according to [11].
  • a liquid crystal display device comprising the color filter according to [12].
  • FIG. 1A and 1B are diagrams for explaining the shape of the substantially cylindrical spacer pattern of the embodiment, and FIG. 1A is a plan view of the spacer pattern, and FIG. ) Is a cross-sectional view of a spacer pattern.
  • (meth) acrylic acid means that both acrylic acid and methacrylic acid are included, and (meth) acrylic, (meth) acrylate, (meth) acryloyl groups, and the like have the same meaning.
  • (co) polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “(acid) anhydride”, “(anhydrous) ... acid”. "Is meant to include both acids and anhydrides.
  • the term “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense.
  • the “total solid content” indicates the total of all components other than the solvent contained in the colored photosensitive composition of the present invention.
  • a method for forming colored spacers having different heights by photolithography is a method mainly characterized by an exposure mask in an exposure process.
  • the exposure mask has a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings.
  • a method of using is known. This has a light-shielding layer (light transmittance 0%) and a plurality of openings, and averages over the opening having the highest average light transmittance (usually light transmittance 100%, hereinafter referred to as a perfect transmission opening).
  • an exposure mask having an opening having a small light transmittance average light transmittance is more than 0% and less than 100%, preferably more than 5% and less than 50%, hereinafter referred to as an intermediate transmission opening.
  • the degree of cure of the formed pattern depends on the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. Differences can be made and then colored spacers of different heights can be formed through development and thermosetting processes.
  • the colored photosensitive composition according to the present invention comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, ( e) a colored photosensitive composition used for collectively forming colored spacers having different heights by a photolithography method, comprising a solvent, and (f) a dispersant, (B) the alkali-soluble resin includes at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2); (F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included, (D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7, The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by
  • a pigment is usually used as the colorant.
  • various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene
  • various inorganic pigments can be used. It is.
  • specific examples of usable pigments are indicated by pigment numbers. Terms 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 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6. *
  • 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.
  • 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.
  • black pigments examples include perylene black (BASF K0084, K0086), cyanine black, and first black HB (C.I. 26150).
  • a single black color material or a black color material obtained by mixing red, green, blue and the like can be used.
  • These black color materials can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.
  • Examples of commercially available carbon black include the following brands. Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc. Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Sck, 350, 350, S350, 250, 350
  • the colored photosensitive composition of the present invention includes (a) the following red pigment as (1) as a colorant, and at least one of the following (2) blue pigment and the following (3) purple pigment: It is preferable from the viewpoint of light shielding properties.
  • C.I. I. Red pigments selected from among pigment reds 177 and 254 (2) C.I. I. Blue pigment which is a pigment blue 15: 6 (3) C.I. I. Among the purple pigments that are the pigment bio red 23, inclusion of (1) and (2) is preferable from the viewpoint of securing the electric retention of the liquid crystal, controlling the level difference, and adhesion to the substrate.
  • the content ratio of (a) the colorant is preferably 35% by weight or less, and less than 30% by weight based on the total solid content in the colored photosensitive composition. Is more preferable. If it is 35% by weight or less, the difference ( ⁇ H) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is preferably increased. If it is less than 30% by weight, the difference ( ⁇ H) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening exceeds 0.35 ⁇ m. A preferred range is 5% to 28% by weight, more preferably 10% to 25% by weight.
  • alkali-soluble resin (A-1) used in the present invention is an ⁇ , ⁇ -unsaturated monocarboxylic acid or ester moiety having an ⁇ , ⁇ -containing ester group on an epoxy resin.
  • An unsaturated monocarboxylic acid ester is added, and a polybasic acid anhydride is further reacted to provide alkali solubility.
  • Such a reaction product has substantially no epoxy group due to its chemical structure.
  • cresol novolac type epoxy resin cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolak type epoxy resin,
  • An epoxy resin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, or the like that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin can be suitably used.
  • the molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC) and is expressed in terms of polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) as Mw, usually in the range of 200 to 200,000, preferably 300 to 100,000. It is. When the molecular weight is less than the above range, it may be difficult to obtain a preferable Mw alkali-soluble resin (A-1). Conversely, when the molecular weight exceeds the above range, ⁇ , ⁇ -unsaturated monocarboxylic acid Gelation is likely to occur during the addition reaction, and production may be difficult.
  • Mw polystyrene-equivalent weight average molecular weight
  • ⁇ , ⁇ -unsaturated monocarboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, and the like. Acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly rich in reactivity. preferable.
  • ⁇ , ⁇ -unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include 2-succinoyloxyethyl acrylate, 2-maleinoyloxyethyl acrylate, and 2-phthaloyloxy acrylate.
  • Ethyl acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexa And hydrophthaloyloxyethyl and crotonic acid-2-succinoyloxyethyl.
  • the addition reaction between an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety and an epoxy resin can be carried out using a known method.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is 0.5 to 1.2 relative to 1 equivalent of the epoxy group of the raw material epoxy resin. A range of equivalents is preferable, and a range of 0.7 to 1.1 equivalents is more preferable.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid anhydride The reaction may be insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, ⁇ , ⁇ -unsaturated monocarboxylic acid or ester thereof may remain as an unreacted product. In either case, the curing characteristics of the coating film may be deteriorated.
  • the alkali-soluble resin (A-1).
  • examples thereof include a method of reacting, for example, a novolac resin and an unsaturated group-containing epoxy compound.
  • a known method can also be used for the addition reaction of polybasic acid anhydride.
  • the addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 mgKOH / g to 150 mgKOH / g, and more preferably in the range of 20 mgKOH / g to 140 mgKOH / g. preferable.
  • the acid value is below the above range, the alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-1) used in the present invention is usually 1500 or more, preferably 2000 or more, usually 50000 or less, Preferably it is 30000 or less, More preferably, it is 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A-1) is too small, the sensitivity tends to decrease, and if it is too large, the solubility in the developer may be insufficient.
  • the alkali-soluble resin (A-2) used in the present invention is obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and It is obtained by reacting a polyhydric alcohol and a polybasic acid anhydride. All components other than the synthesis method and polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-1) can be used for the synthesis of the alkali-soluble resin (A-2).
  • the alkali-soluble resin (A-2) is usually a reaction obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin.
  • the product is obtained by mixing a polyhydric alcohol and a polybasic acid anhydride with heating. In this case, the mixing order of the polyhydric alcohol and the polybasic acid anhydride is not particularly limited.
  • Examples of the polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-2) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that it is 1 type, or 2 or more types of polyhydric alcohol chosen.
  • a polyhydric alcohol By using a polyhydric alcohol, it is possible to increase the molecular weight of the alkali-soluble resin (A-2), introduce branching into the molecule, and balance the molecular weight and viscosity. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.
  • the amount of polyhydric alcohol used is usually about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight with respect to the reaction product with the ⁇ , ⁇ -unsaturated monocarboxylic acid ester component.
  • the acid value of the alkali-soluble resin (A-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient.
  • the acid value is excessively high, there is a problem with the alkali resistance of the colored photosensitive composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). It is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
  • the weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-2) is preferably 1,500 or more, and more preferably 2,000 or more. . Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating strength, and alkali resistance, and if it is too large, a problem may occur in developability and re-solubility.
  • the total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% by weight or more. More preferably, it is 30% by weight or more, usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. If the proportion of the alkali-soluble resin is too much within this range, the developability is lowered, and at the same time, the proportion of the pigment is too small, so that the necessary light-shielding properties tend not to be ensured. May not be possible.
  • an alkali-soluble resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) may be used in combination.
  • Photopolymerization initiator is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat. Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
  • An imidazole derivative of Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
  • Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; Benzanthrone derivatives;
  • Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- Acetophenone derivatives such as (p-butylphenyl) ketone; Thioxanthone derivatives such as thioxanthone,
  • Phenazine derivatives such as 9,10-dimethylbenzphenazine; Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di
  • oxime derivatives As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity, which is disadvantageous in terms of sensitivity when using an alkali-soluble resin containing a phenolic hydroxyl group. Therefore, oxime derivatives (oxime and ketoxime compounds) excellent in such sensitivity are particularly useful.
  • the oxime compound include a compound including a structural moiety represented by the following general formula (2), and preferably include an oxime ester compound represented by the following general formula (3).
  • R 2 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number.
  • R 1a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms.
  • R 1b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
  • R 1a may form a ring together with R 1b , and the linking group may be an alkylene group having 1 to 10 carbon atoms which may have a substituent, a polyethylene group (— (CH ⁇ CH) r -), A polyethynylene group (-(C ⁇ C) r- ), or a group formed by a combination thereof (where r is an integer of 0 to 3).
  • R 2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms.
  • R 2 in the general formula (2) and R 2a in the general formula (3) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 to 8 carbon atoms. Of the cycloalkanoyl group.
  • R 1a in the general formula (3) is preferably an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.
  • R 1b in the general formula (3) is preferably a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, or a phenyl sulfide group which may be substituted.
  • oxime ester-based compound suitable for the present invention include compounds exemplified below, but are not limited to these compounds.
  • ketoxime compounds include compounds containing a structural moiety represented by the following general formula (4), and preferably oxime ester compounds represented by the following general formula (5).
  • R 4 has the same meaning as R 2 in the formula (2).
  • R 3a is a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms, which may be substituted.
  • R 3b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
  • R 3a may form a ring together with R 3b , and each of the linking groups thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH ⁇ CH) r -), A polyethynylene group (-(C ⁇ C) r- ), or a group formed by a combination thereof (where r is an integer of 0 to 3).
  • R 4a is optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group.
  • R 4 in the general formula (4) and R 4a in the general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.
  • R 3a in the general formula (5) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
  • R ⁇ 3b> in the said General formula (5) Preferably the carbazoyl group which may be substituted and the phenyl sulfide group which may be substituted are mentioned.
  • ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but are not limited to these compounds.
  • oxime and ketoxime ester compounds are known per se, such as a series of compounds described in Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 2006-36750. It is a kind.
  • the said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
  • the ratio of the photopolymerization initiator in the light-shielding photosensitive resin composition of the present invention is usually 0.4 to 15% by weight, preferably 0.5 to 10% by weight, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developability tends to be lowered, while if it is too small, the preferred voltage holding ratio, the shape of the colored spacer, and the formation of a step may not be formed.
  • the colored photosensitive composition according to the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7.
  • the alkali-soluble resin in this case means the total of all alkali-soluble resins including at least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2).
  • the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is usually 1 or more, preferably 1.5 or more, more preferably 2 or more, preferably 6 or less, and more preferably 5 or less. If it is 7 or more, the required step may not be formed, and if it is too small, the developability may be deteriorated. When a large amount of alkali-soluble resin having a long dissolution time with respect to the developer is used, the developability may be lowered even if it is 7 or more.
  • Ethylenically unsaturated compound Said photoinitiator is used with an ethylenically unsaturated compound.
  • an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith.
  • the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.
  • the voltage holding ratio it is preferable for the voltage holding ratio to use a compound having three or more ethylenically unsaturated bonds in the molecule.
  • the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.
  • the compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates.
  • esters of unsaturated carboxylic acids and polyhydroxy compounds include (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates.
  • examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
  • esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
  • Reaction product of unsaturated carboxylic acid and sugar alcohol specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
  • Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above.
  • Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
  • Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.
  • Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
  • esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts. And the reaction product.
  • R 10 represents a hydrogen atom or a methyl group
  • p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.
  • p and p ′ are preferably 1 to 10, particularly 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.
  • urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound examples include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate.
  • aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tri Aromatic polyisocyanates such as (isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like. *
  • Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, and “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol
  • Duranate 24A-100 “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate
  • Biuret type same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted.
  • epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound examples include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as ruthenium,
  • ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds in which the ether bond of the ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to change to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No.
  • a polyfunctional (meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organo described in JP-A-9-100111, etc.
  • silica sol (Nissan Chemical Co., Ltd.) MEK-ST ”), methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by NISSAN CHEMICAL CO., LTD.)] And the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent.
  • silica sol Nisan Chemical Co., Ltd.
  • MIBK-ST methyl isobutyl ketone-dispersed organosilica sol
  • MIBK-ST methyl isobutyl ketone-dispersed organosilica sol
  • examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding a silica sol with a functional unsaturated compound via a silane coupling agent.
  • ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Those having 5 or more functional groups are particularly preferable.
  • the above ethylenically unsaturated compounds may be used alone or in combination of two or more.
  • the ratio of the ethylenically unsaturated compound in the light-shielding photosensitive resin composition of the present invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, particularly preferably 12 to 30% by weight, based on the total solid content. It is. If the ratio of the ethylenically unsaturated compound is too much within this range, the developability tends to be lowered. On the other hand, if the amount is too small, it tends to be difficult to ensure the voltage holding ratio and to form the colored spacer and the step. In the present invention, the above-mentioned alkali-soluble resin is not included in the ethylenically unsaturated compound.
  • solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no.
  • the content of the solvent is not particularly limited, but is usually 90% by weight or less and usually 60% by weight from the viewpoint of ease of application during film formation and film thickness control.
  • the content is preferably 70% by weight or more. That is, the colored photosensitive composition of the present invention is preferably prepared so that the total solid content concentration is usually 10% by weight or more, usually 40% by weight or less, particularly 30% by weight or less.
  • a dispersant is used to improve the dispersibility and dispersion stability of the colorant.
  • an acrylic block copolymer containing a nitrogen atom is used as a dispersant.
  • the acrylic block copolymer containing such nitrogen atoms has a nitrogen atom contained therein having an affinity for the colorant surface, and a portion other than the nitrogen atom increases the affinity for the medium. It is estimated that it contributes to the improvement of dispersion stability.
  • the performance of a dispersant is its adsorption behavior on the solid surface.
  • the reason why the block copolymer is excellent in adsorption behavior is not clear in detail, but the following is presumed. That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically at the time of copolymerization. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may become an obstacle when adsorbing to the colorant.
  • a portion that prevents adsorption of the dispersant can be arranged at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorbing portion between the colorant and the dispersing agent, and a portion suitable for it can be arranged in a portion requiring solvent affinity.
  • the dispersion of a colorant containing a colorant having a small crystallite size is presumed to have an effect on good dispersibility due to this molecular arrangement.
  • the acrylic block copolymer includes an AB block copolymer consisting of an A block having at least one of a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group. At least one of a polymer and a BAB block copolymer is preferable.
  • the quaternary ammonium base is preferably —N + R 21 R 22 R 23 • M ⁇ (wherein R 21 , R 22 and R 23 are each independently hydrogen Represents an atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R 21 , R 22 and R 23 may be bonded to each other to form a cyclic structure; M ⁇ represents a counter anion.
  • the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.
  • a cyclic structure formed by combining two or more of R 21 , R 22 and R 23 with each other for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned.
  • the nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the following are mentioned, for example.
  • These cyclic structures may further have a substituent.
  • R represents any group of R 21 to R 23.
  • R 21 - R 23 in -N + R 21 R 22 R 23 more preferred are an alkyl group of 1-3 1 carbon atoms which may have a substituent, which may have a substituent phenyl Or a benzyl group which may have a substituent.
  • the A block having a quaternary ammonium base is particularly preferably one containing a partial structure represented by the following general formula (VI).
  • R 21 , R 22 and R 23 each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R 21 , R 22 and Two or more of R 23 may be bonded to each other to form a cyclic structure, R 24 represents a hydrogen atom or a methyl group, X represents a divalent linking group, M ⁇ represents Represents a counter anion.
  • the hydrocarbon groups of R 21 , R 22 , and R 23 are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. preferable.
  • Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.
  • examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R 25 —, —COO—R 26 — (provided that R 25 and R 26 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R 27 —O—R 28 —: R 27 and R 28 are each independently an alkylene group).
  • -COO-R 26 - is preferable.
  • examples of the counter anion M ⁇ include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , and PF 6 — .
  • the partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks.
  • two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
  • the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. *
  • the content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.
  • the A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that has not been quaternized.
  • the amino group may be any one of primary to tertiary.
  • the content ratio of the monomer having a primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol in the monomer composition constituting the acrylic block copolymer. % Or more.
  • This amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.
  • the primary to tertiary amino group is preferably —NR 41 R 42 (wherein R 41 and R 42 are each independently a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable.
  • R 41 and R 42 are each independently a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable.
  • R 41 and R 42 are each independently a cyclic or chain alkyl group which may have a substituent
  • An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable.
  • a structure represented by the general formula can be given.
  • R 41 and R 42 have the same meanings as R 41 and R 42 described above, R 43 represents an alkylene group having 1 or more carbon atoms, and R 44 represents a hydrogen atom or a methyl group.
  • R 41 and R 42 are preferably a methyl group
  • R 43 is preferably a methylene group or an ethylene group
  • R 44 is preferably a hydrogen atom or a methyl group.
  • a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.
  • the partial structure containing the said amino group may be contained 2 or more types in one A block.
  • the two or more amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
  • a partial structure not containing an amino group may be partially contained in the A block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. .
  • the content of such a partial structure not containing an amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.
  • the A block may have either one of a quaternary ammonium base or an amino group, or may have both.
  • the solubility of a quaternary ammonium base is low and the solubility of an amino group is high in a solvent with low polarity. Therefore, when many solvents with low polarity are used in the resist, from the viewpoint of improving the solubility of the dispersant in the resist solvent, the A block has a quaternary ammonium base and an amino group or quaternary ammonium. It preferably has an amino group without a group, and more preferably has an amino group without a quaternary ammonium group.
  • the B block constituting the acrylic block copolymer has no quaternary ammonium base and amino group described above, and is composed of a monomer that can be copolymerized with the monomer constituting the A block described above.
  • the B block is a solvophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .
  • B block examples include styrene monomers such as styrene and ⁇ -methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic.
  • R 41 represents a hydrogen atom or a methyl group.
  • R 42 may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.
  • Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block.
  • the B block may further contain a partial structure other than these.
  • each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
  • the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block is preferably Is from 0 to 99% by weight, more preferably from 0 to 85% by weight.
  • the acrylic dispersant used in the present invention is an AB block or BAB block copolymer type polymer compound composed of such an A block and a B block. Such a block copolymer Is prepared, for example, by a living polymerization method.
  • the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method.
  • the amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the A block has a quaternary ammonium base and when it does not. It is different.
  • the amine value is a value expressed in mg of KOH corresponding to the molar equivalent of acid necessary for neutralizing the amino group in 1 g of the copolymer.
  • the amount of the quaternary ammonium base in 1 g of the copolymer is Usually, it is preferably 0.1 to 10 mmol, and outside this range, it may not be possible to combine good heat resistance and dispersibility.
  • Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 80 mgKOH / g. . More preferably, it is 1 to 50 mgKOH / g.
  • the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH / g. Hereinafter, it is more preferably 90 to 150 mgKOH / g.
  • the acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g. g or less, more preferably 40 mgKOH / g or less.
  • the molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC.
  • Mw weight average molecular weight
  • the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by weight or more and 90% by weight or less, preferably 5% by weight or more and 60% by weight or less based on the pigment. Or 5 to 40% by weight. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too much, the proportion of other components will decrease and the voltage holding ratio will decrease. On the other hand, the shape of the colored spacer and the formation of the step may not be possible.
  • a dispersant other than an acrylic block copolymer containing a nitrogen atom may be used in combination.
  • the dispersant used in combination is preferably a polymer dispersant, and is preferably a polymer having a completely different structure from the colorant.
  • dispersant used in combination examples include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene diester-based dispersant, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • the dispersion aid means a pigment derivative or the like for improving the dispersibility of the colorant.
  • pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable.
  • substituent of the pigment derivative examples include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group, an aryl group, a complex Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
  • the pigment derivative examples include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
  • These pigment derivatives can be used alone or in combination of two or more.
  • the amount used is usually from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, more preferably from 0.1 to 10% by weight, still more preferably from 0.1 to 30% by weight based on the pigment. 1 to 5% by weight.
  • the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, and a storage.
  • a stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be contained.
  • Photoacid generator is a compound capable of generating an acid by ultraviolet rays.
  • a crosslinking agent such as a melamine compound. If there is, it will advance a crosslinking reaction.
  • photoacid generators those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive composition, are preferable.
  • Crosslinking agent A cross-linking agent can be further added to the colored photosensitive composition of the present invention, and for example, a melamine or guanamine compound can be used.
  • crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).
  • R 61 represents a —NR 66 R 67 group or aryl, and when R 61 is a —NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 ) And when R 61 is aryl, one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group, and R 62 , R 63 , R 64 , R 65 , R 66 and R 67 The rest independently of one another represent hydrogen or a —CH 2 OR 68 group, where R 68 represents hydrogen or alkyl.
  • the aryl is typically phenyl, 1-naphthyl or 2-naphthyl, and a substituent such as alkyl, alkoxy or halogen may be bonded to the phenyl or naphthyl.
  • Alkyl and alkoxy can each have about 1 to 6 carbon atoms.
  • alkyl represented by R 68 is generally methyl or ethyl, particularly methyl.
  • Melamine compounds corresponding to the general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.
  • R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is aryl
  • one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group.
  • R 62 , R 63 , R 64 , R 65 , R 66 and the rest of R 67 independently of one another represent hydrogen or a —CH 2 OR 68 group, where R 68 represents hydrogen or alkyl.
  • guanamine compounds corresponding to the general formula (XI), that is, compounds in which R 61 in the general formula (XI) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.
  • a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below. 2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
  • crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the amount when the crosslinking agent is used is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the light-shielding photosensitive resin composition.
  • the light-shielding photosensitive resin composition of the present invention may contain an adhesion improver in order to sufficiently adhere fine lines and dots.
  • an adhesion improver a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent or the like is preferable.
  • the compound containing a nitrogen atom include diamines (described in Japanese Patent Application Laid-Open No. 11-184080). And other azoles are preferred.
  • azoles are preferable, and in particular, imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improvement described in JP-A-2000-171968). Agents, etc.), and imidazoles and benzimidazoles are most preferred.
  • 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion.
  • -Aminoimidazole is preferred, with 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole and imidazole being particularly preferred.
  • silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.
  • the blending ratio varies depending on the type of adhesion improver used, but is 0.01 to 5% by weight, particularly 0.05%, based on the total solid content of the colored photosensitive composition. It is preferable to set it to 3% by weight. If it is less than this, sufficient adhesion improving effect may not be obtained, and if it is too much, developability may be lowered.
  • Sensitizing dyes examples include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335.
  • JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56 No. 03 Japanese Laid-Open Patent Publication No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088, Japanese Laid-Open Patent Publication No. 5-107761, Japanese Laid-Open Patent Publication No. 5-210240, Japanese Laid-Open Patent Publication No. 4-4.
  • Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-288818.
  • the content of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, the sensitization effect may not be obtained, and if it is too much, the developability may be lowered.
  • surfactant As the surfactant, one or more of various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. It is preferable to use an ionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.
  • the blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0. 0% by weight with respect to the total solid content in the colored photosensitive composition. It is in the range of 5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the addition amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may be exhibited. It may get worse.
  • the colored photosensitive composition of the present invention is at least one of an organic carboxylic acid and an organic carboxylic anhydride for the purpose of improving developability and improving background stains. May be included.
  • the organic carboxylic acid include at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid.
  • aliphatic carboxylic acid examples include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid.
  • dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid
  • tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid.
  • aromatic carboxylic acid examples include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include a carboxylic acid in which a carboxyl group is directly bonded to a group, and a carboxylic acid in which a carboxyl group is bonded from a phenyl group through a carbon bond. *
  • organic carboxylic acids monocarboxylic acids and dicarboxylic acids are preferable, and among them, malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
  • the molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving background stains may be insufficient.
  • Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride.
  • Specific examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, and anhydrous Trifluoroacetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene anhydride
  • Examples thereof include aliphatic carboxylic acid anhydrides such as 2,3-dicarboxylic acid.
  • Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride.
  • the organic carboxylic acid anhydrides maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
  • the molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving background stains may be insufficient.
  • One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.
  • the addition amount of these organic carboxylic acid and organic carboxylic acid anhydride is usually 0.01% by weight to 5% by weight, preferably 0.03% in the total solid content of the light-shielding photosensitive resin composition of the present invention. % By weight to 3% by weight. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.
  • thermal polymerization inhibitor for example, one or more of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, ⁇ -naphthol and the like are used.
  • the blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight based on the total solid content in the light-shielding photosensitive resin composition. Sensitivity may be reduced.
  • plasticizer examples include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. It is done.
  • the blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the light-shielding photosensitive resin composition.
  • a pigment dispersion is produced using (a) a pigment, (f) a dispersant and necessary components.
  • the pigment dispersion obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent are mixed to give a colored photosensitive composition. Manufacturing. You may mix the other above-mentioned component as needed.
  • a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used.
  • a sand grinder it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. Since the pigment is finely divided by this dispersion treatment, the colored photosensitive composition using the pigment dispersion is improved in plate making performance such as coating characteristics and linearity.
  • the alkali-soluble resin or the like When dispersing the pigment, the alkali-soluble resin or the like may be used in combination as appropriate.
  • the temperature during the dispersion treatment is usually set in the range of 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C.
  • the appropriate dispersion time depends on the composition of the pigment dispersion (pigment, solvent, dispersant / dispersion aid, etc.), the size of the sand grinder apparatus, and the like.
  • the content of the pigment (a) in the pigment dispersion is usually 5% by weight to 50% by weight, and preferably 10% by weight to 40% by weight.
  • the content of the dispersant (f) in the pigment dispersion is usually 5% by weight to 90% by weight, preferably 5% by weight to 60% by weight, more preferably 5% by weight, based on the pigment. It is 40 weight or less.
  • the content of the dispersion aid in the pigment dispersion is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably based on the pigment. Is 0.1 to 5% by weight.
  • the content of the alkali-soluble resin (b) in the pigment dispersion is usually 0 to 100% by weight, preferably 5 to 80% by weight, more preferably 5% by weight based on the pigment. % To 60% by weight.
  • the pigment dispersion (ink) obtained by the above dispersion treatment and the above-mentioned other components necessary as a colored photosensitive composition component are added and mixed with stirring to obtain a uniform colored photosensitive composition solution.
  • fine dust is often mixed in the liquid. Therefore, it is desirable to filter the obtained colored photosensitive composition solution with a filter or the like.
  • the coloring photosensitive composition using other than a pigment (for example, dye) as a coloring agent can be manufactured by a well-known method.
  • the colored photosensitive composition of the present embodiment is used in the same manner as a known colored photosensitive composition for a color filter. explain. Usually, a colored photosensitive composition solution is supplied into a film or pattern by a method such as coating on a substrate on which a colored spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a photolithography method in which exposure and development are performed. Then, if necessary, a colored spacer is formed on the substrate by performing additional exposure or thermosetting treatment.
  • the colored photosensitive composition of the present embodiment is usually supplied onto a substrate in a state 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.
  • the usage amount of the coating liquid is greatly reduced, and there is no influence of mist adhering when the spin coating method is used. It is preferable from the viewpoint.
  • the coating amount varies depending on the application.
  • 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 variation is large, a nonuniformity defect occurs in the liquid crystal panel.
  • it may be supplied in a pattern by an ink jet method or a printing method.
  • a known substrate such as a glass substrate can be used as the substrate.
  • the substrate surface is preferably a flat surface.
  • Drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, IR oven, or 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, the performance of the dryer used, and the like.
  • 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 method The exposure is performed by superimposing a negative mask pattern on the coating film of the colored photosensitive composition and irradiating an ultraviolet or visible light source through the mask pattern.
  • the exposure mask When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the colored photosensitive composition, or the exposure mask is placed at a position away from the coating film of the colored photosensitive composition, and the exposure is performed.
  • 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.
  • an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer or in a deoxygenated atmosphere. Or you may.
  • the light source used for the above exposure is not particularly limited.
  • the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, 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 used by irradiating light of a specific wavelength. *
  • the optical filter for example, a thin film type that can control the light transmittance at the exposure wavelength may be used, and as a material in that case, for example, Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), MoSi, Si, W, Al, etc. are mentioned.
  • the exposure mask includes a light shielding layer that blocks light transmission and an opening portion that transmits light, and a part of the opening portions.
  • an exposure mask whose average light transmittance is smaller than the average light transmittance of other openings that is, an opening having a light shielding layer (light transmittance 0%) and a plurality of openings, and having the highest average light transmittance
  • a method using an exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a portion (usually 100% light transmission, hereinafter referred to as a complete transmission opening) can be used.
  • the above optical filter is arbitrarily arranged in the opening (translucent part) of the mask pattern, that is, the opening provided with the optical filter (intermediate transmission opening) and the opening not provided.
  • a method using a mask in which portions (completely transmissive openings) are appropriately arranged can be employed. This makes it possible to form patterns with different photopolymerization rates in accordance with the light transmittance of the openings by a single exposure process, for example, simultaneously forming patterns having different heights in a single exposure process. Is possible. *
  • the light shielding portion and the complete transmission portion are formed in a fine matrix pattern shape or a fine slit pattern shape.
  • the exposure mask having an intermediate transmission opening whose average light transmittance is adjusted (the light transmission is smaller than that of the complete transmission opening) can be formed.
  • the exposure amount in the present embodiment usually, 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 Hereinafter, it is 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, and usually 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 300 ⁇ m 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 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
  • the 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 method is not particularly limited, but is usually performed at a development temperature of 10 ° C. to 50 ° C., preferably 15 ° C. to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. .
  • thermosetting treatment conditions are such that the temperature is selected 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 colored photosensitive composition of the present embodiment is a colored photosensitive composition that is suitably used when forming a black matrix, an overcoat, a rib, a colored spacer, and the like in a color filter such as a liquid crystal display.
  • a colored photosensitive composition suitable for a method for simultaneously forming colored spacers having different heights by a photolithography method can be provided.
  • a high-quality color filter, a liquid crystal display device, and the like can be provided.
  • the colored spacer formed from the colored photosensitive composition of the present invention preferably has a substantially cylindrical spacer pattern.
  • the lower cross-sectional diameter of the colored spacer pattern of the complete transmission opening is usually more than 15 ⁇ m and less than 45 ⁇ m, preferably more than 18 ⁇ m and less than 40 ⁇ m. If it is lower than this range, the compression characteristics tend to be poor, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.
  • the lower cross-sectional diameter of the colored spacer pattern of the intermediate transmission opening is usually more than 20 ⁇ m and less than 50 ⁇ m, preferably more than 30 ⁇ m and less than 40 ⁇ m. If it is lower than this range, the compression characteristics tend to be poor, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.
  • the difference ( ⁇ H) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is that the height of the colored spacer pattern in the completely transmissive opening exceeds 2.8 ⁇ m and less than 3.2 ⁇ m.
  • it is usually 0.25 ⁇ m or more and 1.0 ⁇ m or less, preferably 0.35 ⁇ m or more and 0.80 ⁇ m or less, more preferably 0.4 ⁇ m or more and 0.6 ⁇ m or less.
  • the load resistance tends to deteriorate
  • the compression limit tends to be exceeded.
  • Color filter of the present invention includes the above-described colored spacer of the present invention. For example, a black matrix and red, green, and blue pixel coloring layers on a glass substrate as a transparent substrate. And an overcoat layer are laminated to form a colored spacer, and then an alignment film is formed.
  • a resin film such as polyimide is suitable.
  • liquid crystal display device of the present invention is provided with a color filter having the colored spacer of the present invention as described above.
  • a liquid crystal cell is formed by laminating the above color filter and a liquid crystal driving side substrate. Form. Manufactured by injecting liquid crystal into the formed liquid crystal cell.
  • the present embodiment will be described more specifically with reference to examples and comparative examples.
  • the present embodiment is not limited to the following examples unless it exceeds the gist.
  • the components of the colored photosensitive composition used in the following examples and comparative examples are as follows. In the following, “part” represents “part by weight”.
  • ⁇ Alkali-soluble resin-4> In a 500 mL four-necked flask, 61.2 g of styrene / acrylic acid resin, Jonkrill 680 (BASF Japan Ltd.) was uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 ° C. To this, 0.24 g of tetraammonium chloride and 0.09 g of p-methoxyphenol were added and dissolved. 71.4 g of propylene glycol monomethyl ether acetate and 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400 Daicel Chemical Co., Ltd.) 19 .9 g of the mixed solution was dropped over 40 minutes. The reaction solution was stirred for 32 hours while maintaining at 80 ° C. to obtain a resin having a weight average molecular weight of 6700 and an acid value of 106 mgKOH / g.
  • Examples 1 to 3 Comparative Examples 1 to 4
  • the pigment dispersion prepared above and the components shown in Table 2 were blended in the proportions shown in Table 2 and stirred to prepare colored photosensitive composition coating solutions.
  • a substantially cylindrical spacer pattern was formed by the method described later, and the shape, level difference, adhesion to the substrate, and voltage holding ratio (VHR) were evaluated. The results are shown in Table 2.
  • the said photosensitive composition was apply
  • the obtained coating film was subjected to exposure treatment using an exposure mask having a circular transmission pattern having a circular pattern with a diameter of 15 ⁇ m and an intermediate transmission opening having a circular pattern with a diameter of 35 ⁇ m.
  • the intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 12.1% at a wavelength of 365 nm, a light transmittance of 405 nm at 16.5%, and a light transmittance at 436 nm of 19.6%. .
  • the light transmittance before and after the three points is continuous, and there is no inflection point.
  • the exposure gap (distance between the mask and the coated surface) was 250 ⁇ m. Further, ultraviolet rays having an intensity at 365 nm of 32 mW / cm 2 were used. The exposure amount was 50 mJ / cm 2 . Moreover, ultraviolet irradiation was performed under air.
  • FIGS. 1A and 1B are diagrams for explaining the shape of the substantially cylindrical spacer pattern.
  • the colored spacer pattern 1 is formed in a convex shape on a glass substrate 2 and has a substantially circular outline in plan view.
  • FIG. 1B is an XX cross-sectional view through the central axis 3 of the colored spacer pattern 1 of FIG.
  • the colored spacer pattern 1 has a substantially rectangular outline.
  • Such an outline is defined as a profile 4 of the colored spacer pattern 1
  • intersections between the pattern side surface 41 of the profile 4 and the glass substrate 2 are defined as intersections A and A '.
  • the distance from the surface of the glass substrate 2 to the highest point of the profile 4 is the pattern height H, and the distance between the intersection A and the intersection A ′ is the lower cross-sectional diameter L.
  • the size of the intermediate transmission opening is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35.
  • 24 patterns of different sizes were formed using a mask provided with 24 intermediate transmission openings of 40, 45, and 50 ⁇ m. The size (diameter) of the smallest intermediate transmission aperture where no 24 patterns disappeared was measured. Those having a size of 15 ⁇ m or less were rated as “ ⁇ ” and those having a size exceeding 15 ⁇ m were rated as “ ⁇ ”. The results are shown in Table 2.
  • VHR voltage holding ratio
  • Each colored photosensitive composition solution was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked at 110 ° C. for 70 s on a hot plate to obtain a coating film having a dry film thickness of 3.5 ⁇ m. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed using 3 kW high-pressure mercury under exposure conditions of 50 mJ / cm 2 .
  • shower development with a water pressure of 0.15 MPa was performed at 25 ° C. using an approximately 0.1 wt% potassium hydroxide aqueous solution at 25 ° C., and then development was stopped with pure water and rinsed with a water spray.
  • the shower development time was adjusted between 10 and 120 seconds, and was about 1.6 times the time (break time) for dissolving and removing the photosensitive layer. Those that did not melt even after 120 seconds could not be developed.
  • the electrode substrate thus image-formed was post-baked at 230 ° C. for 20 minutes to obtain a resist-coated electrode substrate (resist substrate). Thereafter, a polyimide solution was applied to the resist substrate, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes.
  • the resist substrate thus obtained was cut into a 2.5 cm square substrate to complete an evaluation electrode substrate A.
  • a polyimide solution was applied also onto the electrode substrate B, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes to complete an evaluation electrode substrate B.
  • an epoxy resin sealant containing silica beads having a diameter of 5 ⁇ m is applied on the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A for evaluation is placed on the front side (the sealant side) of the electrode substrate B.
  • the application surface was pasted and bonded to complete the empty cell. Heating was performed at 180 ° C. for 2 hours in a hot air circulating furnace.
  • a liquid crystal (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.
  • VHR voltage holding ratio
  • the formation of the shape of the completely transmissive opening portion and the intermediate transmissive opening portion pattern, the control of the level difference, the good adhesion, and the liquid crystal voltage holding ratio are excellent. It can be seen that it is possible to obtain colored spacers, which is useful for a method of forming colored spacers having different heights at once.
  • the colored photosensitive composition of the present invention is a colored photosensitive composition that is suitably used when forming a colored spacer or the like in a color filter such as a liquid crystal display, and is a colored spacer having a different height by a photolithography method in particular. In the case of forming all together, it is excellent in shape formation, level difference, adhesion, and liquid crystal electrical reliability.
  • the present invention can provide a high-quality color filter, a liquid crystal display device, and the like.

Abstract

The purpose of the present invention is to provide a colored photosensitive resin composition for ensuring the electric retention rate of the liquid crystals, as well as affording excellent formation of desired shapes, control of difference in level, and cohesion to the substrate, in a method for batch formation of colored spacers of different heights by a photolithography process. The invention relates to a colored photosensitive resin composition employed for batch formation of colored spacers of different heights by a photolithography process, containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.

Description

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Colored photosensitive composition, colored spacer, color filter, and liquid crystal display device
　本発明は、着色感光性組成物等に関する。より詳しくは、例えば液晶ディスプレイ等のカラーフィルターにおいて着色スペーサ等に好ましく用いられる着色感光性組成物及びこれにより形成される着色スペーサ、カラーフィルター、液晶表示装置に関する。 The present invention relates to a colored photosensitive composition and the like. More specifically, the present invention relates to a colored photosensitive composition that is preferably used as a colored spacer in a color filter such as a liquid crystal display, and a colored spacer, a color filter, and a liquid crystal display device formed thereby.
　液晶ディスプレイ（ＬＣＤ）は液晶への電圧のオン・オフにより液晶分子の並び方が切り替わる性質を利用している。一方、ＬＣＤのセルを形成する各部材は、フォトリソグラフィーに代表される感光性組成物を利用して形成されるものが多い。微細な構造を形成し易い、大画面用の基板に対しての処理がし易いといった理由からも、今後さらに感光性組成物の適用範囲は広がる傾向である。　 Liquid crystal display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off the voltage to the liquid crystal. On the other hand, each member forming an LCD cell is often formed using a photosensitive composition typified by photolithography. The range of application of the photosensitive composition tends to further expand in the future because it is easy to form a fine structure and it is easy to process a substrate for a large screen. *
　しかしながら、感光性組成物を用いたＬＣＤでは、感光性組成物自体の電気的特性や、感光性組成物中に含まれる不純物の影響で、液晶にかかる電圧が保持されず、これによってディスプレイの表示ムラといった問題が発生する。特に、カラー液晶表示装置における液晶層により近い部材、例えば、液晶パネルにおいて２枚の基板の間隔を一定に保つために使用されているもの、所謂、柱状スペーサ、フォトスペーサなどではその影響は大きい。 However, in an LCD using a photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, thereby causing display display. Problems such as unevenness occur. Particularly, a member closer to the liquid crystal layer in a color liquid crystal display device, for example, a so-called columnar spacer, photospacer, or the like used to keep the distance between two substrates constant in a liquid crystal panel has a great influence.
　従来、スペーサをＴＦＴ型ＬＣＤに使用する場合、ＴＦＴに入射する光によりスイッチング素子としてＴＦＴが誤作動を起こすことがあった。これを防止するため、例えば、特許文献１にスペーサを遮光性とすることが記載されている。 Conventionally, when a spacer is used for a TFT-type LCD, the TFT may malfunction as a switching element due to light incident on the TFT. In order to prevent this, for example, Patent Document 1 describes that a spacer is made light-shielding.
　また、近年、スペーサをフォトリソグラフィー法により製造するに際して、パネルの構造の変化に伴い、高さの異なるスペーサを一括形成する方法が提案されている。特許文献２には、露光量と残膜率をコントロールすることによって、所望の高さの異なるスペーサの形状、段差を実現できることが開示されている。 In recent years, when manufacturing spacers by a photolithography method, a method has been proposed in which spacers having different heights are collectively formed as the structure of the panel changes. Patent Document 2 discloses that the spacer shape and level difference having different desired heights can be realized by controlling the exposure amount and the remaining film ratio.
日本国特開平８－２３４２１２号公報Japanese Unexamined Patent Publication No. 8-234212 日本国特開２００９－３１７７８号公報Japanese Unexamined Patent Publication No. 2009-31778
　しかしながら、特許文献１に記載のように、スペーサを遮光性にするためには、通常顔料を含めた着色剤等を感光性組成物に添加することが考えられるが、着色剤を添加するにつれクリア成分の減少によりスペーサ層の硬化性が減ること及び顔料に由来する不純物等の影響により、電気特性を損なう恐れがある。 However, as described in Patent Document 1, in order to make the spacer light-shielding, it is conceivable to add a colorant or the like including a pigment to the photosensitive composition, but it is clear as the colorant is added. There is a possibility that the electrical properties may be impaired due to the decrease in the curability of the spacer layer due to the decrease in the components and the influence of impurities derived from the pigment.
　また、特許文献２は顔料を添加しないスペーサに関するもので、顔料を添加する着色スペーサの一括形成に適用すると、顔料が光重合に寄与する紫外領域の光を吸収するため、開口部の光透過率が少ないパターンでは硬化性が劣り、所望の高さの異なるスペーサの形状、段差のコントロール、基板との密着性等の特性を達成することは困難であることが判明した。 Further, Patent Document 2 relates to a spacer to which no pigment is added, and when applied to the batch formation of colored spacers to which a pigment is added, the pigment absorbs light in the ultraviolet region contributing to photopolymerization, and thus the light transmittance of the opening. It has been found that a pattern having a small number has poor curability, and it is difficult to achieve characteristics such as spacer shapes having different heights, step control, and adhesion to a substrate.
　本発明は、このような事情に鑑みてなされたものである。即ち、本発明の主たる課題は、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する為の方法において、液晶の電圧保持率を確保する上、所望の形状の形成、段差のコントロール、基板との密着性に優れた着色感光性組成物を提供することにある。　
　また、本発明の他の課題は、このような着色感光性組成物により形成された着色スペーサを提供することにある。　 The present invention has been made in view of such circumstances. That is, the main problem of the present invention is that in the method for forming colored spacers having different heights by photolithography, the liquid crystal voltage holding ratio is ensured, the formation of a desired shape, the control of the step, the substrate and An object of the present invention is to provide a colored photosensitive composition having excellent adhesion.
Another object of the present invention is to provide a colored spacer formed from such a colored photosensitive composition.
　また更に、本発明の他の課題は、このような着色スペーサを備えるカラーフィルターを提供することにある。　
　また更に、本発明の他の課題は、このようなカラーフィルターを備える液晶表示装置を提供することにある。
　また更に、本発明の他の課題は、このような着色感光性組成物を用いて、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する方法を提供することにある。 Still another object of the present invention is to provide a color filter having such a colored spacer.
Still another object of the present invention is to provide a liquid crystal display device having such a color filter.
Still another object of the present invention is to provide a method for collectively forming colored spacers having different heights using such a colored photosensitive composition by a photolithography method.
　本発明者らは、上記課題について鋭意検討した結果、特定のアルカリ可溶性樹脂及び分散剤を使用し、かつエチレン性不飽和化合物に対するアルカリ可溶性樹脂の重量比及び特定のアルカリ可溶性樹脂の含有割合を特定の範囲とすることにより、上記課題を解決できることを見出し、本発明を完成するに至った。即ち、本発明の要旨は以下の通りである。
［１］　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成するために用いられる着色感光性組成物であって、
　（ｂ）アルカリ可溶性樹脂として、下記アルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）のうち少なくとも一方を含み、
　（ｆ）分散剤として、窒素原子を含有するアクリル系ブロック共重合体を含み、
　（ｄ）エチレン性不飽和化合物に対する（ｂ）アルカリ可溶性樹脂の重量比が、７未満であり、
　着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合が１２重量％以上である着色感光性組成物。　
＜アルカリ可溶性樹脂（Ａ－１）＞
　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸無水物を反応させることにより得られる樹脂
＜アルカリ可溶性樹脂（Ａ－２）＞
　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール及び多塩基酸無水物を反応させることにより得られる樹脂
［２］　着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合が２０重量％以上である上記［１］に記載の着色感光性組成物。
［３］　（ａ）着色剤の含有比率が、着色感光性組成物中の全固形分に対し３０重量％未満である上記［１］又は［２］に記載の着色感光性組成物。
［４］　（ａ）着色剤の含有比率が、着色感光性組成物中の全固形分に対し２５重量％以上である上記［１］乃至［３］のいずれか１つに記載の着色感光性組成物。
［５］　（ａ）着色剤として、以下の（１）赤色顔料を含み、かつ以下の（２）青色顔料及び以下の（３）紫色顔料のうち少なくとも一方を含む上記［１］乃至［４］のいずれか１つに記載の着色感光性組成物。
　　（１）Ｃ．Ｉ．ピックメントレッド１７７、２５４から選ばれる赤色顔料
　　（２）Ｃ．Ｉ．ピックメントブルー１５：６である青色顔料
　　（３）Ｃ．Ｉ．ピックメントバイオレッド２３である紫色顔料
［６］　（ａ）着色剤として、Ｃ．Ｉ．ピックメントレッド２５４及びＣ．Ｉ．ピックメントブルー１５：６を含む上記［１］乃至［４］のいずれか１つに記載の着色感光性組成物。
［７］　（ｆ）分散剤として、側鎖に４級アンモニウム塩基及びアミノ基のうち少なくとも一方を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む上記［１］乃至［６］のいずれか１つに記載の着色感光性組成物。
［８］　（ｆ）分散剤として、側鎖に４級アンモニウム塩基及びアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む上記［１］乃至［６］のいずれか１つに記載の着色感光性組成物。
［９］（ｆ）分散剤として、側鎖に４級アンモニウム塩基を有さずアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む上記［１］乃至［６］のいずれか１つに記載の着色感光性組成物。
［１０］　（ｃ）光重合開始剤として、オキシムエステル化合物を含む上記［１］乃至［９］のいずれか１つに記載の着色感光性組成物。
［１１］　上記［１］乃至［１０］のいずれか１つに記載の着色感光性組成物により一括形成された高さの異なる着色スペーサ。
［１２］　上記［１１］に記載の着色スペーサを備えるカラーフィルター。
［１３］　上記［１２］に記載のカラーフィルターを備える液晶表示装置。
［１４］　上記［１］乃至［１０］のいずれか１つに記載の着色感光性組成物を用いて、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する方法。 As a result of intensive studies on the above problems, the present inventors use a specific alkali-soluble resin and a dispersant, and specify the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and the content ratio of the specific alkali-soluble resin. By setting it as the range of this, it discovered that the said subject could be solved and came to complete this invention. That is, the gist of the present invention is as follows.
[1] Photolithography containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. A colored photosensitive composition used to collectively form colored spacers having different heights by a method,
(B) the alkali-soluble resin includes at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2);
(F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
(D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7,
A colored photosensitive composition in which the total proportion of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition is 12% by weight or more.
<Alkali-soluble resin (A-1)>
Resin obtained by adding α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to epoxy resin, and further reacting with a polybasic acid anhydride <Alkali-soluble resin (A-2)>
Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. [2] The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition [2] is 20% by weight or more. The colored photosensitive composition described in 1.
[3] The colored photosensitive composition according to the above [1] or [2], wherein the content ratio of (a) the colorant is less than 30% by weight with respect to the total solid content in the colored photosensitive composition.
[4] The colored photosensitivity according to any one of [1] to [3], wherein (a) the content ratio of the colorant is 25% by weight or more based on the total solid content in the colored photosensitive composition. Composition.
[5] The above [1] to [4] including (a) the following (1) red pigment and at least one of the following (2) blue pigment and the following (3) purple pigment as the colorant: The coloring photosensitive composition as described in any one of these.
(1) C.I. I. Red pigments selected from among pigment reds 177 and 254 (2) C.I. I. Blue pigment which is a pigment blue 15: 6 (3) C.I. I. Purple pigment [6], which is a pigment bio red 23 (a) As a colorant, C.I. I. Pickment Red 254 and C.I. I. The colored photosensitive composition according to any one of the above [1] to [4], which includes a pigment blue 15: 6.
[7] (f) AB block comprising, as a dispersant, an A block having at least one of a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group The colored photosensitive composition according to any one of the above [1] to [6], comprising at least one of a copolymer and a BAB block copolymer.
[8] (f) As a dispersant, an AB block copolymer comprising an A block having a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group, and The colored photosensitive composition according to any one of the above [1] to [6], comprising at least one of BAB block copolymers.
[9] (f) As a dispersant, an AB block consisting of an A block having an amino group without a quaternary ammonium base in the side chain, and a B block having no quaternary ammonium base and an amino group. The colored photosensitive composition according to any one of the above [1] to [6], comprising at least one of a polymer and a BAB block copolymer.
[10] The colored photosensitive composition according to any one of the above [1] to [9], which contains an oxime ester compound as a photopolymerization initiator (c).
[11] Colored spacers having different heights, which are collectively formed from the colored photosensitive composition according to any one of [1] to [10].
[12] A color filter comprising the colored spacer according to [11].
[13] A liquid crystal display device comprising the color filter according to [12].
[14] A method of collectively forming colored spacers having different heights by a photolithography method using the colored photosensitive composition according to any one of [1] to [10].
　本発明によれば、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する為の方法において、液晶の電気保持率を確保する上、所望の形状の形成、段差のコントロール、基板との密着性を実現することが出来る。 According to the present invention, in a method for collectively forming colored spacers having different heights by photolithography, it is possible to ensure the electrical retention of liquid crystal, to form a desired shape, to control a step, and to adhere to a substrate. Can be realized.
図１（Ａ）及び図１（Ｂ）は、実施例の略円柱状スペーサパターンの形状を説明するための図であり、図１（Ａ）はスペーサパターンの平面図であり、図１（Ｂ）はスペーサパターンの断面図である。1A and 1B are diagrams for explaining the shape of the substantially cylindrical spacer pattern of the embodiment, and FIG. 1A is a plan view of the spacer pattern, and FIG. ) Is a cross-sectional view of a spacer pattern.
　以下、本発明を実施するための形態について詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を超えない限り、これらの内容に特定されない。
　なお、本発明において、「（メタ）アクリル酸」とは、アクリル酸とメタクリル酸の双方を含むことを意味し、（メタ）アクリル、（メタ）アクリレート、（メタ）アクリロイル基なども同様の意味であり、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、「（酸）無水物」、「（無水）…酸」とは、酸とその無水物の双方を含むことを意味する。
　また、本発明において「モノマー」とは、いわゆる高分子物質に相対する意味であり、狭義の単量体（モノマー）の外に、二量体、三量体、オリゴマー等も含む意味である。なお、ここで、「全固形分」とは、本発明の着色感光性組成物に含まれる溶剤以外のすべての成分の合計を示す。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. , Not specified in these contents.
In the present invention, “(meth) acrylic acid” means that both acrylic acid and methacrylic acid are included, and (meth) acrylic, (meth) acrylate, (meth) acryloyl groups, and the like have the same meaning. And “(co) polymer” means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “(acid) anhydride”, “(anhydrous) ... acid”. "Is meant to include both acids and anhydrides.
In the present invention, the term “monomer” has a meaning corresponding to a so-called polymer substance, and includes a dimer, a trimer, an oligomer and the like in addition to a monomer (monomer) in a narrow sense. Here, the “total solid content” indicates the total of all components other than the solvent contained in the colored photosensitive composition of the present invention.
　［１］高さの異なる着色スペーサの一括形成方法
　フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する為の方法は、主として露光工程における露光マスクに特徴を有する方法である。　
　その露光マスクとして、光の透過を遮る遮光層と光を透過させる複数の開口部とを有し、一部の開口部の平均光透過率が他の開口部の平均光透過率より小さい露光マスクを用いる方法が知られている。これは、遮光層（光透過率０％）と複数の開口部を有し、平均光透過率の最も高い開口部（通常、光透過率１００％。以下完全透過開口部という）に対して平均光透過率の小さい開口部（平均光透過率が０％超過１００％未満。好ましくは、５％超過５０％未満。以下中間透過開口部という）、を有する露光マスクを用いる方法である。この方法により、例えばネガ型の着色感光性組成物の場合であれば、中間透過開口部と完全透過開口部の平均光透過率の差異、即ち露光量の差異により、形成したパターンの硬化度の差異を生じさせ、その後、現像及び熱硬化プロセスを経て高さの異なる着色スペーサを形成することができる。 [1] Batch forming method of colored spacers having different heights A method for forming colored spacers having different heights by photolithography is a method mainly characterized by an exposure mask in an exposure process.
As an exposure mask, the exposure mask has a light shielding layer that blocks light transmission and a plurality of openings that transmit light, and the average light transmittance of some openings is smaller than the average light transmittance of other openings. A method of using is known. This has a light-shielding layer (light transmittance 0%) and a plurality of openings, and averages over the opening having the highest average light transmittance (usually light transmittance 100%, hereinafter referred to as a perfect transmission opening). This is a method using an exposure mask having an opening having a small light transmittance (average light transmittance is more than 0% and less than 100%, preferably more than 5% and less than 50%, hereinafter referred to as an intermediate transmission opening). With this method, for example, in the case of a negative type colored photosensitive composition, the degree of cure of the formed pattern depends on the difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, the difference in exposure amount. Differences can be made and then colored spacers of different heights can be formed through development and thermosetting processes.
　［２］着色感光性組成物
　本発明に係る着色感光性組成物は、（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成するために用いられる着色感光性組成物であって、
　（ｂ）アルカリ可溶性樹脂として、下記アルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）のうち少なくとも一方を含み、
　（ｆ）分散剤として、窒素原子を含有するアクリル系ブロック共重合体を含み、
　（ｄ）エチレン性不飽和化合物に対する（ｂ）アルカリ可溶性樹脂の重量比が、７未満であり、
　着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合が１２重量％以上であることを特徴とする。　
　＜アルカリ可溶性樹脂（Ａ－１）＞
　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸無水物を反応させることにより得られる樹脂。
　＜アルカリ可溶性樹脂（Ａ－２）＞
　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール及び多塩基酸無水物を反応させることにより得られる樹脂。 [2] Colored photosensitive composition The colored photosensitive composition according to the present invention comprises (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, ( e) a colored photosensitive composition used for collectively forming colored spacers having different heights by a photolithography method, comprising a solvent, and (f) a dispersant,
(B) the alkali-soluble resin includes at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2);
(F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
(D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7,
The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more.
<Alkali-soluble resin (A-1)>
Resin obtained by adding α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to epoxy resin, and further reacting with a polybasic acid anhydride .
<Alkali-soluble resin (A-2)>
Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. Resin obtained by
　　［２－１］　（ａ）着色剤
　着色剤としては、通常顔料が用いられる。顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構造としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系等の有機顔料の他に種々の無機顔料等も利用可能である。以下、使用できる顔料の具体例をピグメントナンバーで示す。以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。 [2-1] (a) Colorant A pigment is usually used as the colorant. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene, various inorganic pigments can be used. It is. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. Terms such as “CI Pigment Red 2” mentioned below mean the color index (CI).
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１６８、１７７、２０２、２０６、２０７、２０９、２２４、２４２、２５４、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。　 As red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, 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. *
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー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を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。　 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. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6. *
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６を挙げることができる。　 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. *
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー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、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、さらに好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。　 ¡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, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, 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. *
　オレンジ顔料としては、Ｃ．Ｉ．ピグメントオレンジ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を挙げることができる。この中でも、好ましくは、Ｃ．Ｉ．ピグメントオレンジ３８、７１を挙げることができる。　 】 As orange pigment, 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. Of these, C.I. I. And CI pigment oranges 38 and 71. *
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。　 As purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23. *
　黒色顔料として、ペリレンブラック（ＢＡＳＦ　Ｋ００８４、Ｋ００８６）、シアニンブラック、ファーストブラックＨＢ（Ｃ．Ｉ．２６１５０）を挙げることができる。　
　本発明の着色感光性組成物には単独の黒色色材、又は赤、緑、青色等の混合による黒色色材が使用可能である。これら黒色色材は、カーボンブラック、チタンブラックなどの無機又は有機の顔料、染料の中から適宜選択することができ、単独使用もしくは複数種混合して使用することができる。 Examples of black pigments include perylene black (BASF K0084, K0086), cyanine black, and first black HB (C.I. 26150).
In the colored photosensitive composition of the present invention, a single black color material or a black color material obtained by mixing red, green, blue and the like can be used. These black color materials can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.
　カーボンブラックの市販品の例としては、以下のような銘柄が挙げられる。　
　三菱化学社製：ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ２２０、ＭＡ２３０、＃５２、＃５０、＃４７、＃４５、＃２７００、＃２６５０、＃２２００、＃１０００、＃９９０、＃９００等。　
　デグサ社製：Ｐｒｉｎｔｅｘ９５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３、ＰｒｉｎｔｅｘＡ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００等。　 Examples of commercially available carbon black include the following brands.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.
Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, Sck, 350, 350, S350, 250, 350
　キャボット社製：Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ４３０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ１２０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＢＬＡＣＫＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０。　 Made by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS 480S. *
　コロンビヤンカーボン社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１５、ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０等。　
　チタンブラックの市販品の例としては、三菱マテリアル社製チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃなどが挙げられる。　
　本発明の着色感光性組成物は、（ａ）着色剤として、以下の（１）の赤色顔料を含み、かつ以下の（２）の青色顔料及び以下の（３）の紫色顔料のうち少なくとも一方を含むことが、遮光性の観点から好ましい。 Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040 and the like.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, and 13M-C manufactured by Mitsubishi Materials Corporation.
The colored photosensitive composition of the present invention includes (a) the following red pigment as (1) as a colorant, and at least one of the following (2) blue pigment and the following (3) purple pigment: It is preferable from the viewpoint of light shielding properties.
　　（１）Ｃ．Ｉ．ピックメントレッド１７７、２５４から選ばれる赤色顔料
　　（２）Ｃ．Ｉ．ピックメントブルー１５：６である青色顔料
　　（３）Ｃ．Ｉ．ピックメントバイオレッド２３である紫色顔料
　中でも、（１）と（２）を含むことが、液晶の電気保持率の確保、段差のコントロール、基板との密着性の観点から好ましい。また、Ｃ．Ｉ．ピックメントレッド２５４及びＣ．Ｉ．ピックメントブルー１５：６を含むことが、可視光領域の遮光性が向上する観点から好ましい。 (1) C.I. I. Red pigments selected from among pigment reds 177 and 254 (2) C.I. I. Blue pigment which is a pigment blue 15: 6 (3) C.I. I. Among the purple pigments that are the pigment bio red 23, inclusion of (1) and (2) is preferable from the viewpoint of securing the electric retention of the liquid crystal, controlling the level difference, and adhesion to the substrate. In addition, C.I. I. Pickment Red 254 and C.I. I. It is preferable that the pigment blue 15: 6 is included from the viewpoint of improving the light blocking property in the visible light region.
　本発明の着色感光性組成物では、（ａ）着色剤の含有比率が、該着色感光性組成物中の全固形分に対し３５重量％以下であることが好ましく、３０重量％未満であることがより好ましい。３５重量％以下だと完全透過開口部の着色スペーサパターンの高さと中間透過開口部の着色スペーサパターンの高さの差異（ΔＨ）が大きくなり好ましい。３０重量％未満だと完全透過開口部の着色スペーサパターンの高さと中間透過開口部の着色スペーサパターンの高さの差異（ΔＨ）が０．３５μｍを超える。好ましい範囲は５重量％～２８重量％であり、更に好ましくは１０重量％～２５重量％である。（ａ）着色剤の含有比率が大きすぎると、着色感光性組成物の感度が落ち、所望の高さの異なるスペーサの形状、段差の形成ができない場合がある。一方、着色剤の含有比率が小さすぎる場合には、着色スペーサとしての十分な遮光性が確保できない場合がある。 In the colored photosensitive composition of the present invention, the content ratio of (a) the colorant is preferably 35% by weight or less, and less than 30% by weight based on the total solid content in the colored photosensitive composition. Is more preferable. If it is 35% by weight or less, the difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is preferably increased. If it is less than 30% by weight, the difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening exceeds 0.35 μm. A preferred range is 5% to 28% by weight, more preferably 10% to 25% by weight. (A) When the content ratio of the colorant is too large, the sensitivity of the colored photosensitive composition is lowered, and there may be a case where spacers having different heights and steps cannot be formed. On the other hand, when the content ratio of the colorant is too small, there may be a case where sufficient light shielding properties as the colored spacer cannot be ensured.
　［２－２］（ｂ）アルカリ可溶性樹脂
　本発明に用いるアルカリ可溶性樹脂（Ａ－１）は、エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、更に多塩基酸無水物を反応させることによりアルカリ可溶性を付与する等の方法で得られる。かかる反応生成物は化学構造上、実質的にエポキシ基を有さない。 [2-2] (b) Alkali-soluble resin The alkali-soluble resin (A-1) used in the present invention is an α, β-unsaturated monocarboxylic acid or ester moiety having an α, β-containing ester group on an epoxy resin. An unsaturated monocarboxylic acid ester is added, and a polybasic acid anhydride is further reacted to provide alkali solubility. Such a reaction product has substantially no epoxy group due to its chemical structure.
　原料となるエポキシ樹脂として、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、ジシクロペンタジエンとフェノールまたはクレゾールとの重付加反応物とエピハロヒドリンとの反応生成物であるエポキシ樹脂、アダマンチル基含有エポキシ樹脂、フルオレン型エポキシ樹脂等を好適に用いることができる。 As the raw material epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthalene novolak type epoxy resin, An epoxy resin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, or the like that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin can be suitably used.
　エポキシ樹脂の分子量は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）で測定してポリスチレン換算重量平均分子量（以下「Ｍｗ」という）として、Ｍｗとして、通常２００～２０万、好ましくは３００～１０万の範囲である。分子量が上記範囲未満である場合には、好ましいＭｗのアルカリ可溶性樹脂（Ａ－１）を得られ難いことがあり、逆に上記範囲を越えた場合にはα，β－不飽和モノカルボン酸の付加反応時にゲル化が起こりやすく製造が困難となるおそれがある。 The molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC) and is expressed in terms of polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) as Mw, usually in the range of 200 to 200,000, preferably 300 to 100,000. It is. When the molecular weight is less than the above range, it may be difficult to obtain a preferable Mw alkali-soluble resin (A-1). Conversely, when the molecular weight exceeds the above range, α, β-unsaturated monocarboxylic acid Gelation is likely to occur during the addition reaction, and production may be difficult.
　α，β－不飽和モノカルボン酸としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、桂皮酸等が挙げられ、好ましくはアクリル酸及びメタクリル酸であり、特にアクリル酸が反応性に富むため好ましい。また、エステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとしては、アクリル酸－２－サクシノイルオキシエチル、アクリル酸－２－マレイノイルオキシエチル、アクリル酸－２－フタロイルオキシエチル、アクリル酸－２－ヘキサヒドロフタロイルオキシエチル、メタクリル酸－２－サクシノイルオキシエチル、メタクリル酸－２－マレイノイルオキシエチル、メタクリル酸－２－フタロイルオキシエチル、メタクリル酸－２－ヘキサヒドロフタロイルオキシエチル、クロトン酸－２－サクシノイルオキシエチル等を挙げられる。 Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, and the like. Acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly rich in reactivity. preferable. In addition, α, β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester moiety include 2-succinoyloxyethyl acrylate, 2-maleinoyloxyethyl acrylate, and 2-phthaloyloxy acrylate. Ethyl, acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexa And hydrophthaloyloxyethyl and crotonic acid-2-succinoyloxyethyl.
　α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルとエポキシ樹脂との付加反応は、公知の手法を用いて行うことができる。またα，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルの使用量は、原料エポキシ樹脂のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、さらに好ましくは０．７～１．１当量の範囲である。α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルの使用量が少ないと不飽和基の導入量が不足し、引き続く多塩基酸無水物との反応も不十分となることがある。また多量のエポキシ基が残存することも有利ではない。一方、該使用量が多いとα，β－不飽和モノカルボン酸又はそのエステルが未反応物として残存することがある。いずれの場合も塗膜の硬化特性が悪化する可能性がある。 The addition reaction between an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety and an epoxy resin can be carried out using a known method. The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is 0.5 to 1.2 relative to 1 equivalent of the epoxy group of the raw material epoxy resin. A range of equivalents is preferable, and a range of 0.7 to 1.1 equivalents is more preferable. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid anhydride The reaction may be insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or ester thereof may remain as an unreacted product. In either case, the curing characteristics of the coating film may be deteriorated.
　尚、本発明においては、製造工程としてエポキシ樹脂を経由しなくても、最終的な樹脂の構造が同じであれば本出願においては、それもアルカリ可溶性樹脂（Ａ－１）の範疇であると定義する。その例としては、例えばノボラック樹脂と不飽和基含有エポキシ化合物を反応させる方法が挙げられる。
　エポキシ樹脂にα，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させた生成物に更に付加させる多塩基酸無水物としては、無水マレイン酸、無水コハク酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水ピロメリット酸、無水トリメリット酸、ベンゾフェノンテトラカルボン酸二無水物、無水メチルヘキサヒドロフタル酸、無水エンドメチレンテトラヒドロフタル酸、無水クロレンド酸、無水メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸二無水物等が挙げられ、好ましくは、無水マレイン酸、無水コハク酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水ピロメリット酸、無水トリメリット酸、ビフェニルテトラカルボン酸二無水物であり、特に好ましい化合物は、無水テトラヒドロフタル酸及びビフェニルテトラカルボン酸二無水物である。 In the present invention, even if the production process does not involve an epoxy resin, if the final resin structure is the same, in the present application, this is also a category of the alkali-soluble resin (A-1). Define. Examples thereof include a method of reacting, for example, a novolac resin and an unsaturated group-containing epoxy compound.
As a polybasic acid anhydride to be further added to a product in which an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, Acid, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, end methylenetetrahydro anhydride Examples include phthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, preferably maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride , Pyromellitic anhydride, trimellitic anhydride Biphenyl tetracarboxylic dianhydride, particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic acid dianhydride.
　多塩基酸無水物の付加反応に関しても公知の手法を用いることができる。多塩基酸無水物の付加量は、生成するエポキシアクリレート系樹脂の酸価が１０ｍｇＫＯＨ／ｇ～１５０ｍｇＫＯＨ／ｇの範囲となるのが好ましく、更に２０ｍｇＫＯＨ／ｇ～１４０ｍｇＫＯＨ／ｇの範囲となるのが特に好ましい。酸価が上記範囲以下であるとアルカリ現像性に乏しくなり、また、上記範囲を越えると硬化性能に劣る傾向が認められる。 A known method can also be used for the addition reaction of polybasic acid anhydride. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in the range of 10 mgKOH / g to 150 mgKOH / g, and more preferably in the range of 20 mgKOH / g to 140 mgKOH / g. preferable. When the acid value is below the above range, the alkali developability is poor, and when it exceeds the above range, a tendency to be inferior in curing performance is recognized.
　本発明で用いるアルカリ可溶性樹脂（Ａ－１）の、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の重量平均分子量（Ｍｗ）は通常１５００以上、好ましくは２０００以上であり、通常５００００以下、好ましくは３００００以下、より好ましくは１００００以下である。このアルカリ可溶性樹脂（Ａ－１）の重量平均分子量が小さすぎると、感度が低下する傾向があり、大きすぎると現像液に対する溶解性が不足する場合があるため好ましくない。 The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-1) used in the present invention is usually 1500 or more, preferably 2000 or more, usually 50000 or less, Preferably it is 30000 or less, More preferably, it is 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A-1) is too small, the sensitivity tends to decrease, and if it is too large, the solubility in the developer may be insufficient.
　本発明に用いるアルカリ可溶性樹脂（Ａ－２）は、エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール及び多塩基酸無水物を反応させることにより得られる。
　アルカリ可溶性樹脂（Ａ－１）の合成に用いる合成方法や多価アルコール以外の成分は、全てがアルカリ可溶性樹脂（Ａ－２）の合成に用いることができる。アルカリ可溶性樹脂（Ａ－２）は、通常は、エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させてなる反応物に、多価アルコール及び多塩基酸無水物を混合し、加温することにより得られる。この場合、多価アルコールと多塩基酸無水物の混合順序に、特に制限はない。 The alkali-soluble resin (A-2) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and It is obtained by reacting a polyhydric alcohol and a polybasic acid anhydride.
All components other than the synthesis method and polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-1) can be used for the synthesis of the alkali-soluble resin (A-2). The alkali-soluble resin (A-2) is usually a reaction obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin. The product is obtained by mixing a polyhydric alcohol and a polybasic acid anhydride with heating. In this case, the mixing order of the polyhydric alcohol and the polybasic acid anhydride is not particularly limited.
　アルカリ可溶性樹脂（Ａ－２）の合成に用いる多価アルコールしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールの中から選ばれる１種又は２種以上の多価アルコールであることが好ましい。
　多価アルコールを用いることにより、アルカリ可溶性樹脂（Ａ－２）の分子量を増大させ、分子中に分岐を導入することが出来、分子量と粘度のバランスをとることができる。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスのとれた有機結合剤を得ることができる。 Examples of the polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-2) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that it is 1 type, or 2 or more types of polyhydric alcohol chosen.
By using a polyhydric alcohol, it is possible to increase the molecular weight of the alkali-soluble resin (A-2), introduce branching into the molecule, and balance the molecular weight and viscosity. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.
　多価アルコールの使用量は、少な過ぎると効果が薄く、多過ぎると増粘やゲル化の可能性があるので、エポキシ樹脂成分とα，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステル成分との反応物に対して、通常０．０１～０．５重量倍程度、好ましくは０．０２～０．２重量倍程度である。
　このようにして得られるアルカリ可溶性樹脂（Ａ－２）の酸価は、通常１０ｍｇＫＯＨ／ｇ以上、好ましくは５０ｍｇＫＯＨ／ｇ以上である。酸価が１０ｍｇＫＯＨ／ｇ未満では現像性が不足する場合がある。また酸価が過度に高いと、着色感光性組成物のアルカリ耐性に問題がある（すなわち、アルカリ性現像液により、パターン表面の粗面化や、膜減りが生じる）場合があるので、酸価は２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。 If the amount of polyhydric alcohol used is too small, the effect will be diminished, and if it is too large, there is a possibility of thickening or gelation. The amount is usually about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight with respect to the reaction product with the α, β-unsaturated monocarboxylic acid ester component.
The acid value of the alkali-soluble resin (A-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient. If the acid value is excessively high, there is a problem with the alkali resistance of the colored photosensitive composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). It is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
　アルカリ可溶性樹脂（Ａ－２）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算の重量平均分子量（Ｍｗ）は、１，５００以上であることが好ましく、２，０００以上であることがより好ましい。また、２０，０００以下であることが好ましく、１０，０００以下であることがより好ましい。重量平均分子量が小さ過ぎると感度や塗膜強度、アルカリ耐性に問題が生じる可能性があり、大き過ぎると現像性や再溶解性に問題が生じる場合がある。 The weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A-2) is preferably 1,500 or more, and more preferably 2,000 or more. . Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating strength, and alkali resistance, and if it is too large, a problem may occur in developability and re-solubility.
　本発明の着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合は、１２重量％以上であり、好ましくは２０重量以上％であり、より好ましくは３０重量％以上であり、通常７０重量％以下であり、好ましくは６０重量％以下であり、より好ましくは５０重量％以下である。この範囲よりもアルカリ可溶性樹脂の割合が多過ぎると現像性が低下すると同時に顔料の割合が少なすぎるため必要な遮光性も確保できない傾向があり、一方少な過ぎると所望のスペーサの形状、段差の形成ができない場合がある。　
　アルカリ可溶性樹脂としては、アルカリ可溶性樹脂（Ａ－１）、アルカリ可溶性樹脂（Ａ－２）以外の他のアルカリ可溶性樹脂を併用してもよい。 The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% by weight or more. More preferably, it is 30% by weight or more, usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. If the proportion of the alkali-soluble resin is too much within this range, the developability is lowered, and at the same time, the proportion of the pigment is too small, so that the necessary light-shielding properties tend not to be ensured. May not be possible.
As the alkali-soluble resin, an alkali-soluble resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) may be used in combination.
　［２－３］（ｃ）光重合開始剤　
　本発明に係る光重合開始剤とは、紫外線や熱によりエチレン性不飽和基を重合させるラジカルを発生させることのできる化合物である。　
　本発明で用いることができる光重合開始剤の具体的な例を以下に列挙する。　
　２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジンなどのハロメチル化トリアジン誘導体；
　ハロメチル化オキサジアゾール誘導体；　 [2-3] (c) Photopolymerization initiator
The photopolymerization initiator according to the present invention is a compound capable of generating radicals that polymerize ethylenically unsaturated groups by ultraviolet rays or heat.
Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
Halomethylated oxadiazole derivatives;
　２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体などのイミダゾール誘導体；　
　ベンゾインメチルエーテル、ベンゾインフェニルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテルなどのベンゾイン、ベンゾインアルキルエーテル類；　
　２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノンなどのアントラキノン誘導体；
　ベンズアンスロン誘導体；　 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) ) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, etc. An imidazole derivative of
Benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzanthrone derivatives;
　ベンゾフェノン、ミヒラーケトン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノンなどのベンゾフェノン誘導体；　
　２，２，－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、２－メチル－（４’－（メチルチオ）フェニル）－２－モルホリノ－１－プロパノン、１，１，１－トリクロロメチル－（ｐ－ブチルフェニル）ケトンなどのアセトフェノン誘導体；　
　チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントンなどのチオキサントン誘導体；　
　ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジエチルアミノ安息香酸エチルなどの安息香酸エステル誘導体；　
　９－フェニルアクリジン、９－（ｐ－メトキシフェニル）アクリジンなどのアクリジン誘導体；　 Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2, -dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p- Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
　９，１０－ジメチルベンズフェナジンなどのフェナジン誘導体；　
　ジ－シクロペンタジエニル－Ｔｉ－ジ－クロライド、ジ－シクロペンタジエニル－Ｔｉ－ビス－フェニル、ジ－シクロペンタジエニル－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニ－１－イル、ジ－シクロペンタジエニル－Ｔｉ－ビス－２，３，５，６－テトラフルオロフェニ－１－イル、ジ－シクロペンタジエニル－Ｔｉ－ビス－２，４，６－トリフルオロフェニ－１－イル、ジ－シクロペンタジエニル－Ｔｉ－２，６－ジ－フルオロフェニ－１－イル、ジ－シクロペンタジエニル－Ｔｉ－２，４－ジ－フルオロフェニ－１－イル、ジ－メチルシクロペンタジエニル－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニ－１－イル、ジ－メチルシクロペンタジエニル－Ｔｉ－ビス－２，６－ジ－フルオロフェニ－１－イル、ジ－シクロペンタジエニル－Ｔｉ－２，６－ジ－フルオロ－３－（ピル－１－イル）－フェニ－１－イルなどのチタノセン誘導体；　
　２－メチル－１［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコン等のα－アミノアルキルフェノン系化合物；　 Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluoro Feni-1-i , Di - cyclopentadienyl -Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
　光重合開始剤としては、特に、感度の点でオキシム誘導体類（オキシム系及びケトオキシム系化合物）が有効であり、フェノール性水酸基を含むアルカリ可溶性樹脂を用いる場合などは、感度の点で不利になるため、特にこのような感度に優れたオキシム誘導体類（オキシム系及びケトオキシム系化合物）が有用である。　
　オキシム系化合物としては、下記一般式（２）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（３）で示されるオキシムエステル系化合物が挙げられる。　 As photopolymerization initiators, oxime derivatives (oxime-based and ketoxime-based compounds) are particularly effective in terms of sensitivity, which is disadvantageous in terms of sensitivity when using an alkali-soluble resin containing a phenolic hydroxyl group. Therefore, oxime derivatives (oxime and ketoxime compounds) excellent in such sensitivity are particularly useful.
Examples of the oxime compound include a compound including a structural moiety represented by the following general formula (2), and preferably include an oxime ester compound represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式（２）中、Ｒ２は、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルカノイル基、炭素数２～１０のアミノアルキルカルボニル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基を示す。）　 (In the formula (2), R 2 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number. A cycloalkanoyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, and a group having 2 to 10 carbon atoms An aminoalkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式（３）中、Ｒ１ａは、水素、またはそれぞれ置換されていてもよい、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基を示す。　
　Ｒ１ｂは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。　
　なお、Ｒ１ａはＲ１ｂと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）ｒ－）、ポリエチニレン基（－（Ｃ≡Ｃ）ｒ－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。　
　Ｒ２ａは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシキシカルボニルアルカノイル基、炭素数２～１０のアミノカルボニル基、炭素数炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基又は炭素数７～２０のアリールオキシカルボニル基を示す。）　 (In the formula (3), R 1a is hydrogen or an optionally substituted alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl group having 1 to 20 carbon atoms. , Alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, aminoalkyl having 1 to 20 carbon atoms A alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, An alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.
R 1b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R 1a may form a ring together with R 1b , and the linking group may be an alkylene group having 1 to 10 carbon atoms which may have a substituent, a polyethylene group (— (CH═CH) r -), A polyethynylene group (-(C≡C) r- ), or a group formed by a combination thereof (where r is an integer of 0 to 3).
R 2a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. , Alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, aminocarbonyl group having 2 to 10 carbon atoms, carbon number carbon An aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms. )
　上記一般式（２）におけるＲ２及び上記一般式（３）におけるＲ２ａとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基が挙げられる。　 R 2 in the general formula (2) and R 2a in the general formula (3) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 to 8 carbon atoms. Of the cycloalkanoyl group.
　上記一般式（３）におけるＲ１ａとしては、好ましくは無置換のメチル基、エチル基、プロピル基や、Ｎ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基が挙げられる。
　また、上記一般式（３）におけるＲ１ｂとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいチオキサントニル基、置換されていてもよいフェニルスルフィド基が挙げられる。　 R 1a in the general formula (3) is preferably an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.
In addition, R 1b in the general formula (3) is preferably a carbazoyl group which may be substituted, a thioxanthonyl group which may be substituted, or a phenyl sulfide group which may be substituted.
　本発明に好適なオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 Specific examples of the oxime ester-based compound suitable for the present invention include compounds exemplified below, but are not limited to these compounds.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　ケトオキシム系化合物としては、下記一般式（４）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（５）で示されるオキシムエステル系化合物が挙げられる。 Examples of ketoxime compounds include compounds containing a structural moiety represented by the following general formula (4), and preferably oxime ester compounds represented by the following general formula (5).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（上記一般式（４）において、Ｒ４は、前記一般式（２）におけるＲ２と同義である。） (In the general formula (4), R 4 has the same meaning as R 2 in the formula (2).)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（上記一般式（５）において、Ｒ３ａは、それぞれ置換されていてもよい、フェニル基、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数２～２０のアルキルチオアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基、を示す。　 (In the above general formula (5), R 3a is a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroaryl having 1 to 20 carbon atoms, which may be substituted. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, or a heteroary A ruthioalkyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms. , A heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or 7 carbon atoms To 20 aryloxycarbonyl groups.
　Ｒ３ｂは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。　
　なお、Ｒ３ａはＲ３ｂと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）ｒ－）、ポリエチニレン基（－（Ｃ≡Ｃ）ｒ－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。　 R 3b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R 3a may form a ring together with R 3b , and each of the linking groups thereof may have an optionally substituted alkylene group having 1 to 10 carbon atoms, a polyethylene group (— (CH═CH) r -), A polyethynylene group (-(C≡C) r- ), or a group formed by a combination thereof (where r is an integer of 0 to 3).
　Ｒ４ａは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数４～８のシクロアルカノイル基、炭素数７～２０のベンゾイル基、炭素数３～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、炭素数２～２０のヘテロアリール基、又は炭素数２～２０のアルキルアミノカルボニル基を表す。）　 R 4a is optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, benzoyl group having 7 to 20 carbon atoms, carbon Heteroaryloyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylamino having 2 to 20 carbon atoms Represents a carbonyl group. )
　上記一般式（４）におけるＲ４及び上記一般式（５）におけるＲ４ａとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基が挙げられる。　 R 4 in the general formula (4) and R 4a in the general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, or 3 to 8 carbon atoms. And a cycloalkanoyl group and an aryloyl group having 7 to 20 carbon atoms.
　上記一般式（５）におけるＲ３ａとしては、好ましくは無置換のエチル基、プロピル基、ブチル基や、メトキシカルボニル基で置換されたエチル基またはプロピル基が挙げられる。
　また、上記一般式（５）におけるＲ３ｂとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいフェニルスルフィド基が挙げられる。　 R 3a in the general formula (5) is preferably an unsubstituted ethyl group, propyl group, butyl group, or an ethyl group or propyl group substituted with a methoxycarbonyl group.
Moreover, as R <3b> in the said General formula (5), Preferably the carbazoyl group which may be substituted and the phenyl sulfide group which may be substituted are mentioned.
　本発明に好適なケトオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but are not limited to these compounds.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　これらのオキシム及びケトオキシムエステル系化合物は、それ自体公知の化合物であり、例えば、日本国特開２０００－８００６８号公報や、日本国特開２００６－３６７５０号公報に記載されている一連の化合物の一種である。　
　上記光重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。　
　本発明の遮光性感光性樹脂組成物中の光重合開始剤の割合は、全固形分に対して通常０．４～１５重量％、好ましくは０．５～１０重量％である。この範囲よりも光重合開始剤の割合が多すぎると現像性が低下する傾向があり、一方少なすぎると好ましい電圧保持率や着色スペーサの形状、段差の形成ができない場合がある。 These oxime and ketoxime ester compounds are known per se, such as a series of compounds described in Japanese Unexamined Patent Publication No. 2000-80068 and Japanese Unexamined Patent Publication No. 2006-36750. It is a kind.
The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
The ratio of the photopolymerization initiator in the light-shielding photosensitive resin composition of the present invention is usually 0.4 to 15% by weight, preferably 0.5 to 10% by weight, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developability tends to be lowered, while if it is too small, the preferred voltage holding ratio, the shape of the colored spacer, and the formation of a step may not be formed.
　本発明に係る着色感光性組成物は、エチレン性不飽和化合物に対するアルカリ可溶性樹脂の重量比が７未満であることを特徴とする。この場合のアルカリ可溶性樹脂は、アルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）のうち少なくとも一方を含む全アルカリ可溶性樹脂の合計を意味する。エチレン性不飽和化合物に対するアルカリ可溶性樹脂の重量比は、通常１以上、好ましくは１．５以上、更に好ましくは２以上であり、好ましくは６以下であり、更に好ましい範囲は５以下である。７以上であると必要な段差の形成が出来ない場合があり、少なすぎると現像性が低下する場合がある。現像液に対して溶解時間の長いアルカリ可溶性樹脂を多く使用した場合は、７以上でも現像性が低下する場合がある。 The colored photosensitive composition according to the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7. The alkali-soluble resin in this case means the total of all alkali-soluble resins including at least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is usually 1 or more, preferably 1.5 or more, more preferably 2 or more, preferably 6 or less, and more preferably 5 or less. If it is 7 or more, the required step may not be formed, and if it is too small, the developability may be deteriorated. When a large amount of alkali-soluble resin having a long dissolution time with respect to the developer is used, the developability may be lowered even if it is 7 or more.
　［２－４］（ｄ）エチレン性不飽和化合物　
　上記の光重合開始剤は、エチレン性不飽和化合物と共に用いられる。
　ここで使用されるエチレン性不飽和化合物としては、エチレン性不飽和結合を分子内に１個以上有する化合物を意味するが、重合性、架橋性、及びそれに伴う露光部と非露光部の現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましく、また、その不飽和結合は（メタ）アクリロイルオキシ基に由来する（メタ）アクリレート化合物が更に好ましい。　 [2-4] (d) Ethylenically unsaturated compound
Said photoinitiator is used with an ethylenically unsaturated compound.
As used herein, an ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule, but it is polymerizable, crosslinkable, and a developer for exposed and non-exposed areas associated therewith. From the viewpoint that the difference in solubility can be expanded, the compound is preferably a compound having two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth) acryloyloxy group (meta ) Acrylate compounds are more preferred.
　更に、エチレン性不飽和結合を分子内に３個以上有する化合物を用いると電圧保持率的にとって好ましい。　
　エチレン性不飽和結合を分子内に１個以上有する化合物としては、例えば、（メタ）アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、イタコン酸、シトラコン酸等の不飽和カルボン酸、及びそのアルキルエステル、（メタ）アクリロニトリル、（メタ）アクリルアミド、スチレン等が挙げられる。　 Furthermore, it is preferable for the voltage holding ratio to use a compound having three or more ethylenically unsaturated bonds in the molecule.
Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof. , (Meth) acrylonitrile, (meth) acrylamide, styrene and the like.
　エチレン性不飽和結合を分子内に２個以上有する化合物としては、代表的には、不飽和カルボン酸とポリヒドロキシ化合物とのエステル類、（メタ）アクリロイルオキシ基含有ホスフェート類、ヒドロキシ（メタ）アクリレート化合物とポリイソシアネート化合物とのウレタン（メタ）アクリレート類、及び、（メタ）アクリル酸又はヒドロキシ（メタ）アクリレート化合物とポリエポキシ化合物とのエポキシ（メタ）アクリレート類等が挙げられる。 The compounds having two or more ethylenically unsaturated bonds are typically esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, hydroxy (meth) acrylates. Examples include urethane (meth) acrylates of a compound and a polyisocyanate compound, and epoxy (meth) acrylates of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.
　不飽和カルボン酸とポリヒドロキシ化合物とのエステル類としては、具体的には以下の化合物が挙げられる。　
　不飽和カルボン酸と糖アルコールとの反応物；糖アルコールは具体的には、エチレングリコール、ポリエチレングリコール（付加数２～１４）、プロピレングリコール、ポリプロピレングリコール（付加数２～１４）、トリメチレングリコール、テトラメチレングリコール、ヘキサメチレングリコール、トリメチロールプロパン、グリセロール、ペンタエリスリトール、ジペンタエリスリトール等が挙げられる。　 Specific examples of esters of an unsaturated carboxylic acid and a polyhydroxy compound include the following compounds.
Reaction product of unsaturated carboxylic acid and sugar alcohol; specifically, sugar alcohol includes ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
　不飽和カルボン酸と糖アルコールのアルキレンオキサイド付加物との反応物；糖アルコールは上記と同じ。アルキレンオキサイド付加物とは具体的にはエチレンオキサイド付加物、又はプロピレンオキサイド付加物等が挙げられる。　
　不飽和カルボン酸とアルコールアミンとの反応物；アルコールアミン類とは具体的にはジエタノールアミン、トリエタノールアミン等が挙げられる。　
　具体的な不飽和カルボン酸とポリヒドロキシ化合物とのエステル類は以下の通りである。　 Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol; sugar alcohol is the same as above. Specific examples of the alkylene oxide adduct include an ethylene oxide adduct and a propylene oxide adduct.
Reaction product of unsaturated carboxylic acid and alcohol amine; specific examples of alcohol amines include diethanolamine and triethanolamine.
Specific esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.
　エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド付加トリ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、グリセロールプロピレンオキサイド付加トリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等、及び同様のクロトネート、イソクロトネート、マレエート、イタコネート、シトラコネート等。 Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide addition tri (meta) ) Acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Etc., and the like crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.
　その他の、不飽和カルボン酸とポリヒドロキシ化合物とのエステル類としては、不飽和カルボン酸と、ヒドロキノン、レゾルシン、ピロガロール、ビスフェノールＦ、ビスフェノールＡ等の芳香族ポリヒドロキシ化合物、或いはそれらのエチレンオキサイド付加物との反応物が挙げられる。具体的には、例えば、ビスフェノールＡジ（メタ）アクリレート、ビスフェノールＡビス〔オキシエチレン（メタ）アクリレート〕、ビスフェノールＡビス〔グリシジルエーテル（メタ）アクリレート〕等、また、前記の如き不飽和カルボン酸と、トリス（２－ヒドロキシエチル）イソシアヌレート等の複素環式ポリヒドロキシ化合物との反応物、例えば、トリス（２－ヒドロキシエチル）イソシアヌレートのジ（メタ）アクリレート、トリ（メタ）アクリレート等、また、不飽和カルボン酸と多価カルボン酸とポリヒドロキシ化合物との反応物、例えば、（メタ）アクリル酸とフタル酸とエチレングリコールとの縮合物、（メタ）アクリル酸とマレイン酸とジエチレングリコールとの縮合物、（メタ）アクリル酸とテレフタル酸とペンタエリスリトールとの縮合物、（メタ）アクリル酸とアジピン酸とブタンジオールとグリセリンとの縮合物等が挙げられる。 Other esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcinol, pyrogallol, bisphenol F, bisphenol A, or their ethylene oxide adducts. And the reaction product. Specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc., and the unsaturated carboxylic acid as described above A reaction product with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, such as di (meth) acrylate or tri (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, Reaction product of unsaturated carboxylic acid, polyvalent carboxylic acid and polyhydroxy compound, for example, condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, condensate of (meth) acrylic acid, maleic acid and diethylene glycol , (Meth) acrylic acid, terephthalic acid and pentae Condensates of Suritoru include condensates of (meth) acrylic acid and adipic acid and butane diol and glycerol.
　（メタ）アクリロイルオキシ基含有ホスフェート類としては、下記一般式（６），（７），（８）で表されるものが好ましい。　 As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (6), (7) and (8) are preferable. *
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（６），（７）及び（８）中、Ｒ１０は水素原子又はメチル基を示し、ｐ及びｐ’は１～２５の整数、ｑは１、２、又は３である。）　
　ここで、ｐ及びｐ’は１～１０、特に１～４であるのが好ましく、これらの具体例としては、例えば、（メタ）アクリロイルオキシエチルホスフェート、ビス〔（メタ）アクリロイルオキシエチル〕ホスフェート、（メタ）アクリロイルオキシエチレングリコールホスフェート等が挙げられ、これらはそれぞれが単独で用いられても混合物として用いられてもよい。　 (In the formulas (6), (7) and (8), R 10 represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2 or 3.)
Here, p and p ′ are preferably 1 to 10, particularly 1 to 4, and specific examples thereof include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (Meth) acryloyloxyethylene glycol phosphate and the like may be mentioned, and these may be used alone or as a mixture.
　ヒドロキシ（メタ）アクリレート化合物とポリイソシアネート化合物とのウレタン（メタ）アクリレート類としては、例えば、ヒドロキシメチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、テトラメチロールエタントリ（メタ）アクリレート等のヒドロキシ（メタ）アクリレート化合物と、ヘキサメチレンジイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン等の脂肪族ポリイソシアネート、シクロヘキサンジイソシアネート、ジメチルシクロヘキサンジイソシアネート、４，４－メチレンビス（シクロヘキシルイソシアネート）、イソホロンジイソシアネート、ビシクロヘプタントリイソシアネート等の脂環式ポリイソシアネート、４，４－ジフェニルメタンジイソシアネート、トリス（イソシアネートフェニル）チオホスフェート等の芳香族ポリイソシアネート、イソシアヌレート等の複素環式ポリイソシアネート、等のポリイソシアネート化合物との反応物等が挙げられる。　 Examples of urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound include hydroxy (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylolethane tri (meth) acrylate. ) Acrylate compound, aliphatic polyisocyanate such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptanetri Cycloaliphatic polyisocyanates such as isocyanate, 4,4-diphenylmethane diisocyanate, tri Aromatic polyisocyanates such as (isocyanate phenyl) thiophosphate, heterocyclic polyisocyanates such as isocyanurate, a reaction product of a polyisocyanate compounds and the like. *
　このようなものとしては例えば、新中村化学社製商品名「Ｕ－４ＨＡ」「ＵＡ－３０６Ａ」「ＵＡ－ＭＣ３４０Ｈ」「ＵＡ－ＭＣ３４０Ｈ」「Ｕ６ＬＰＡ」等が挙げられる。　
　これらの中でも、１分子中に４個以上のウレタン結合〔－ＮＨ－ＣＯ－Ｏ－〕及び４個以上の（メタ）アクリロイルオキシ基を有する化合物が好ましく、該化合物は、例えば、ペンタエリスリトール、ポリグリセリン等の１分子中に４個以上の水酸基を有する化合物に、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート等のジイソシアネート化合物を反応させて得られた化合物、或いは、エチレングリコール等の１分子中に２個以上の水酸基を有する化合物に、旭化成工業社製「デュラネート２４Ａ－１００」、同「デュラネート２２Ａ－７５ＰＸ」、同「デュラネート２１Ｓ－７５Ｅ」、同「デュラネート１８Ｈ－７０Ｂ」等ビウレットタイプ、同「デュラネートＰ－３０１－７５Ｅ」、同「デュラネートＥ－４０２－９０Ｔ」、同「デュラネートＥ－４０５－８０Ｔ」等のアダクトタイプ等の１分子中に３個以上のイソシアネート基を有する化合物を反応させて得られた化合物、或いは、イソシアネートエチル（メタ）アクリレート等を重合若しくは共重合させて得られた化合物等の、１分子中に４個以上、好ましくは６個以上のイソシアネート基を有する化合物等、例えば、旭化成工業社製「デュラネートＭＥ２０－１００」と、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の、１分子中に１個以上の水酸基及び２個以上、好ましくは３個以上の（メタ）アクリロイルオキシ基を有する化合物とを、反応させることにより得ることができる。　 Examples of such products include trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, and “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd.
Among these, a compound having 4 or more urethane bonds [—NH—CO—O—] and 4 or more (meth) acryloyloxy groups in one molecule is preferable, and examples of the compound include pentaerythritol, poly A compound obtained by reacting a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate with a compound having 4 or more hydroxyl groups in one molecule such as glycerin, or ethylene glycol As a compound having two or more hydroxyl groups in one molecule, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 18H-70B”, etc. manufactured by Asahi Kasei Kogyo Co., Ltd. Biuret type, same A compound having three or more isocyanate groups in one molecule such as adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T” and “Duranate E-405-80T” is reacted. The compound obtained, or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like, a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, such as Asahi Kasei Kogyo "Duranate ME20-100", pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. 1 or more hydroxyl groups and 2 in one molecule Above, can preferably be obtained by a compound having three or more (meth) acryloyloxy group, it is reacted.
　（メタ）アクリル酸又はヒドロキシ（メタ）アクリレート化合物とポリエポキシ化合物とのエポキシ（メタ）アクリレート類としては、例えば、（メタ）アクリル酸、又は前記の如きヒドロキシ（メタ）アクリレート化合物と、（ポリ）エチレングリコールポリグリシジルエーテル、（ポリ）プロピレングリコールポリグリシジルエーテル、（ポリ）テトラメチレングリコールポリグリシジルエーテル、（ポリ）ペンタメチレングリコールポリグリシジルエーテル、（ポリ）ネオペンチルグリコールポリグリシジルエーテル、（ポリ）ヘキサメチレングリコールポリグリシジルエーテル、（ポリ）トリメチロールプロパンポリグリシジルエーテル、（ポリ）グリセロールポリグリシジルエーテル、（ポリ）ソルビトールポリグリシジルエーテル等の脂肪族ポリエポキシ化合物、フェノールノボラックポリエポキシ化合物、ブロム化フェノールノボラックポリエポキシ化合物、（ｏ－，ｍ－，ｐ－）クレゾールノボラックポリエポキシ化合物、ビスフェノールＡポリエポキシ化合物、ビスフェノールＦポリエポキシ化合物等の芳香族ポリエポキシ化合物、ソルビタンポリグリシジルエーテル、トリグリシジルイソシアヌレート、トリグリシジルトリス（２－ヒドロキシエチル）イソシアヌレート等の複素環式ポリエポキシ化合物、等のポリエポキシ化合物との反応物等が挙げられる。　 Examples of epoxy (meth) acrylates of (meth) acrylic acid or a hydroxy (meth) acrylate compound and a polyepoxy compound include (meth) acrylic acid, or a hydroxy (meth) acrylate compound as described above, and (poly) Ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene Glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether Aliphatic polyepoxy compounds such as ruthenium, phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds Aromatic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, heterocyclic polyepoxy compounds such as triglycidyl tris (2-hydroxyethyl) isocyanurate, and reactants with polyepoxy compounds such as It is done. *
　その他のエチレン性不飽和化合物として、前記以外に、例えば、エチレンビス（メタ）アクリルアミド等の（メタ）アクリルアミド類、フタル酸ジアリル等のアリルエステル類、ジビニルフタレート等のビニル基含有化合物類、エーテル結合含有エチレン性不飽和化合物のエーテル結合を５硫化燐等により硫化してチオエーテル結合に変えることにより架橋速度を向上せしめたチオエーテル結合含有化合物類、及び、例えば、日本国特許第３１６４４０７号公報及び日本国特開平９－１００１１１号公報等に記載の、多官能（メタ）アクリレート化合物と、粒子径５～３０ｎｍのシリカゾル〔例えば、イソプロパノール分散オルガノシリカゾル（日産化学社製「ＩＰＡ－ＳＴ」）、メチルエチルケトン分散オルガノシリカゾル（日産化学社製「ＭＥＫ－ＳＴ」）、メチルイソブチルケトン分散オルガノシリカゾル（日産化学社製「ＭＩＢＫ－ＳＴ」）等〕とを、イソシアネート基或いはメルカプト基含有シランカップリング剤を用いて結合させた化合物等の、エチレン性不飽和化合物にシランカップリング剤を介してシリカゾルを反応させ結合させることにより硬化物としての強度や耐熱性を向上せしめた化合物類、等が挙げられる。　 Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bonds Thioether bond-containing compounds in which the ether bond of the ethylenically unsaturated compound is sulfurized with phosphorus pentasulfide or the like to change to a thioether bond to improve the crosslinking rate, and for example, Japanese Patent No. 3164407 and Japan A polyfunctional (meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (“IPA-ST” manufactured by Nissan Chemical Co., Ltd.)), methyl ethyl ketone-dispersed organo described in JP-A-9-100111, etc. Silica sol (Nissan Chemical Co., Ltd.) MEK-ST ”), methyl isobutyl ketone-dispersed organosilica sol (“ MIBK-ST ”manufactured by NISSAN CHEMICAL CO., LTD.)] And the like, and the like, by using an isocyanate group or a mercapto group-containing silane coupling agent. Examples thereof include compounds in which the strength and heat resistance as a cured product are improved by reacting and bonding a silica sol with a functional unsaturated compound via a silane coupling agent. *
　本発明において、エチレン性不飽和化合物としては、エステル（メタ）アクリレート類、又は、ウレタン（メタ）アクリレート類が好ましく、中でも、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等、５官能以上のものが特に好ましい。
　以上のエチレン性不飽和化合物は、それぞれ単独で用いられてもよく、２種以上が併用されてもよい。　 In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or urethane (meth) acrylates are preferable, and among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Those having 5 or more functional groups are particularly preferable.
The above ethylenically unsaturated compounds may be used alone or in combination of two or more.
　本発明の遮光性感光性樹脂組成物中のエチレン性不飽和化合物の割合は、全固形分に対して通常１～６０重量％、好ましくは５～４０重量％、特に好ましくは１２～３０重量％である。この範囲よりもエチレン性不飽和化合物の割合が多すぎると、現像性が低下する傾向がある。一方少なすぎると電圧保持率の確保や着色スペーサの形状、段差の形成ができにくい傾向がある。
　尚、本発明において、エチレン性不飽和化合物には、上述のアルカリ可溶性樹脂は含まれない。 The ratio of the ethylenically unsaturated compound in the light-shielding photosensitive resin composition of the present invention is usually 1 to 60% by weight, preferably 5 to 40% by weight, particularly preferably 12 to 30% by weight, based on the total solid content. It is. If the ratio of the ethylenically unsaturated compound is too much within this range, the developability tends to be lowered. On the other hand, if the amount is too small, it tends to be difficult to ensure the voltage holding ratio and to form the colored spacer and the step.
In the present invention, the above-mentioned alkali-soluble resin is not included in the ethylenically unsaturated compound.
　［２－５］（ｅ）溶剤　
　以上に示した本発明の着色感光性組成物に含まれる各成分は、通常、溶剤に溶解又は分散させ、着色感光性組成物溶液として用いられる。　
　ここで用いられる溶剤としては、例えば、ジイソプロピルエーテル、ミネラルスピリット、ｎ－ペンタン、アミルエーテル、エチルカプリレート、ｎ－ヘキサン、ジエチルエーテル、イソプレン、エチルイソブチルエーテル、ブチルステアレート、ｎ－オクタン、バルソル＃２、アプコ＃１８ソルベント、ジイソブチレン、アミルアセテート、ブチルアセテート、アプコシンナー、ブチルエーテル、ジイソブチルケトン、メチルシクロヘキセン、メチルノニルケトン、プロピルエーテル、ドデカン、ソーカルソルベントＮｏ．１及びＮｏ．２、アミルホルメート、ジヘキシルエーテル、ジイソプロピルケトン、ソルベッソ＃１５０、（ｎ，ｓｅｃ，ｔ－）酢酸ブチル、ヘキセン、シェルＴＳ２８　ソルベント、ブチルクロライド、エチルアミルケトン、エチルベンゾエート、アミルクロライド、エチレングリコールジエチルエーテル、エチルオルソホルメート、メトキシメチルペンタノン、メチルブチルケトン、メチルヘキシルケトン、メチルイソブチレート、ベンゾニトリル、エチルプロピオネート、メチルセロソルブアセテート、メチルイソアミルケトン、メチルイソブチルケトン、プロピルアセテート、アミルアセテート、アミルホルメート、ビシクロヘキシル、ジエチレングリコールモノエチルエーテルアセテート、ジペンテン、メトキシメチルペンタノール、メチルアミルケトン、メチルイソプロピルケトン、プロピルプロピオネート、プロピレングリコール－ｔ－ブチルエーテル、メチルエチルケトン、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、カルビトール、シクロヘキサノン、酢酸エチル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシプロピオン酸、３－エトキシプロピオン酸、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、ジグライム、エチレングリコールアセテート、エチルカルビトール、ブチルカルビトール、エチレングリコールモノブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、３－メトキシブタノール、３－メチル－３－メトキシブタノール、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブチルアセテート等が挙げられる。これらの溶剤は、１種を単独で使用しても、２種以上を混合して使用してもよい。 [2-5] (e) Solvent
Each component contained in the colored photosensitive composition of the present invention described above is usually dissolved or dispersed in a solvent and used as a colored photosensitive composition solution.
Examples of the solvent used here include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Luketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropion Acid, 3-e Methyl methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, Examples include butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.
　本発明の着色感光性組成物において、溶剤の含有量は、特に制限はないが、塗膜形成時の塗布のし易さや膜厚制御の観点からの通常９０重量％以下で、通常６０重量％以上、特に７０重量％以上であることが好ましい。即ち、本発明の着色感光性組成物においては、全固形分濃度が通常１０重量％以上、通常４０重量％以下、特に３０重量％以下となるように調製されることが好ましい。　 In the colored photosensitive composition of the present invention, the content of the solvent is not particularly limited, but is usually 90% by weight or less and usually 60% by weight from the viewpoint of ease of application during film formation and film thickness control. In particular, the content is preferably 70% by weight or more. That is, the colored photosensitive composition of the present invention is preferably prepared so that the total solid content concentration is usually 10% by weight or more, usually 40% by weight or less, particularly 30% by weight or less. *
　［２－６］　（ｆ）分散剤
　本発明の感光性樹脂組成物は、着色剤の分散性の向上、分散安定性の向上のために、分散剤が使用される。
　本発明では、分散剤として窒素原子を含有するアクリル系ブロック共重合体が用いられる。このような窒素原子を含有するアクリル系ブロック共重合体は、これに含まれる窒素原子が着色剤表面に対して親和性を持ち、窒素原子以外の部分が媒質に対する親和性を高めることにより、全体として分散安定性の向上に寄与するものと推定される。　 [2-6] (f) Dispersant In the photosensitive resin composition of the present invention, a dispersant is used to improve the dispersibility and dispersion stability of the colorant.
In the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant. The acrylic block copolymer containing such nitrogen atoms has a nitrogen atom contained therein having an affinity for the colorant surface, and a portion other than the nitrogen atom increases the affinity for the medium. It is estimated that it contributes to the improvement of dispersion stability.
　分散剤の性能は、その固体表面に対する吸着挙動である。ブッロク共重合体が吸着挙動に優れている理由は、詳しいメカニズムは不明だが、以下のことが推察される。　
　即ち、通常のランダム共重合体の場合、共重合体を構成するモノマーは、共重合時において、立体的に、及び／又は電気的に共重合体中に安定的に配置される確率が高くなる。モノマーが安定的に配置された部分（分子）は、立体的に、及び／又は電気的に安定しているため、着色剤に吸着するとき、かえって障害となる場合がある。これに対し、ブロック共重合体のように分子配列が制御された樹脂は、分散剤の吸着を妨げる部分を、顔料と分散剤との吸着部から離れた位置に配置することができる。つまり、着色剤と分散剤との吸着部には吸着に最適な部分を、溶媒親和性が必要な部分にはそれに適した部分を配置することができる。特に結晶子サイズの小さい着色剤を含有する色材の分散は、この分子配置が良好な分散性に影響するものと推察される。　 The performance of a dispersant is its adsorption behavior on the solid surface. The reason why the block copolymer is excellent in adsorption behavior is not clear in detail, but the following is presumed.
That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high probability of being stably arranged in the copolymer sterically and / or electrically at the time of copolymerization. . Since the portion (molecule) in which the monomer is stably arranged is sterically and / or electrically stable, it may become an obstacle when adsorbing to the colorant. On the other hand, in a resin whose molecular arrangement is controlled, such as a block copolymer, a portion that prevents adsorption of the dispersant can be arranged at a position away from the adsorption portion of the pigment and the dispersant. That is, an optimum portion for adsorption can be arranged in the adsorbing portion between the colorant and the dispersing agent, and a portion suitable for it can be arranged in a portion requiring solvent affinity. In particular, the dispersion of a colorant containing a colorant having a small crystallite size is presumed to have an effect on good dispersibility due to this molecular arrangement.
　窒素原子を含有するアクリル系ブロック共重合体は、本発明に用いられる着色剤を極めて効率よく分散しうる点で好ましい。その理由は明らかではないが、分子配列が制御されていることにより、分散剤が着色剤に吸着する際に障害となる構造が少ないためと推察される。アクリル系ブロック共重合体としては、側鎖に４級アンモニウム塩基及びアミノ基のうち少なくとも一方を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方が好ましい。 An acrylic block copolymer containing a nitrogen atom is preferable in that it can disperse the colorant used in the present invention very efficiently. The reason is not clear, but it is presumed that because the molecular arrangement is controlled, there are few structures that obstruct the dispersing agent when adsorbed to the colorant. The acrylic block copolymer includes an AB block copolymer consisting of an A block having at least one of a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group. At least one of a polymer and a BAB block copolymer is preferable.
　Ａブロックが４級アンモニウム塩基を有する場合、当該４級アンモニウム塩基は、好ましくは－Ｎ＋Ｒ２１Ｒ２２Ｒ２３・Ｍ－（但し、Ｒ２１、Ｒ２２及びＲ２３は、各々独立に、水素原子、又は置換されていてもよい環状若しくは鎖状の炭化水素基を表す。或いは、Ｒ２１、Ｒ２２及びＲ２３のうち２つ以上が互いに結合して、環状構造を形成していてもよい。Ｍ－は、対アニオンを表す。）で表される。この４級アンモニウム塩基は、直接主鎖に結合していてもよいが、２価の連結基を介して主鎖に結合していてもよい。　 When the A block has a quaternary ammonium base, the quaternary ammonium base is preferably —N + R 21 R 22 R 23 • M − (wherein R 21 , R 22 and R 23 are each independently hydrogen Represents an atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R 21 , R 22 and R 23 may be bonded to each other to form a cyclic structure; M − represents a counter anion. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.
　－Ｎ＋Ｒ２１Ｒ２２Ｒ２３において、Ｒ２１、Ｒ２２及びＲ２３のうち２つ以上が互いに結合して形成する環状構造としては、例えば５～７員環の含窒素複素環単環又はこれらが２個縮合してなる縮合環が挙げられる。該含窒素複素環は芳香性を有さないものが好ましく、飽和環であればより好ましい。具体的には、例えば下記のものが挙げられる。これらの環状構造は、更に置換基を有していてもよい。　 In —N + R 21 R 22 R 23 , as a cyclic structure formed by combining two or more of R 21 , R 22 and R 23 with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the following are mentioned, for example. These cyclic structures may further have a substituent.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（上記式中、ＲはＲ２１～Ｒ２３のうち何れかの基を表す。）
　－Ｎ＋Ｒ２１Ｒ２２Ｒ２３におけるＲ２１～Ｒ２３として、より好ましいのは、置換基を有していてもよい炭素数１～３のアルキル基、置換基を有していてもよいフェニル基、又は置換基を有していてもよいベンジル基である。　
　また、４級アンモニウム塩基を有するＡブロックとしては、特に、下記一般式（ＶＩ）で表される部分構造を含有するものが好ましい。　 (In the above formula, R represents any group of R 21 to R 23. )
As R 21 - R 23 in -N + R 21 R 22 R 23 , more preferred are an alkyl group of 1-3 1 carbon atoms which may have a substituent, which may have a substituent phenyl Or a benzyl group which may have a substituent.
In addition, the A block having a quaternary ammonium base is particularly preferably one containing a partial structure represented by the following general formula (VI).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（上記式（ＶＩ）中、Ｒ２１、Ｒ２２、Ｒ２３は各々独立に、水素原子、又は置換されていてもよい環状若しくは鎖状の炭化水素基を表す。或いは、Ｒ２１、Ｒ２２及びＲ２３のうち２つ以上が互いに結合して、環状構造を形成していてもよい。Ｒ２４は、水素原子又はメチル基を表す。Ｘは、２価の連結基を表し、Ｍ－は、対アニオンを表す。）　
　上記一般式（ＶＩ）において、Ｒ２１、Ｒ２２、Ｒ２３の炭化水素基は、それぞれ独立して、炭素数１～１０のアルキル基、炭素数６～２０の芳香族基を有する置換基が好ましい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ベンジル基、フェニル基等を挙げることができる。中でもメチル基、エチル基、プロピル基、ベンジル基が好ましい。　 (In the above formula (VI), R 21 , R 22 and R 23 each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R 21 , R 22 and Two or more of R 23 may be bonded to each other to form a cyclic structure, R 24 represents a hydrogen atom or a methyl group, X represents a divalent linking group, M − represents Represents a counter anion.)
In the general formula (VI), the hydrocarbon groups of R 21 , R 22 , and R 23 are each independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group. Of these, a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.
　上記一般式（ＶＩ）において、２価の連結基Ｘとしては、例えば、炭素数１～１０のアルキレン基、アリーレン基、－ＣＯＮＨ－Ｒ２５－、－ＣＯＯ－Ｒ２６－（但し、Ｒ２５及びＲ２６は、直接結合、炭素数１～１０のアルキレン基、又は炭素数１～１０のエーテル基（－Ｒ２７－Ｏ－Ｒ２８－：Ｒ２７及びＲ２８は、各々独立にアルキレン基）を表す。）等が挙げられ、好ましくは－ＣＯＯ－Ｒ２６－である。　
　また、対アニオンのＭ－としては、Ｃｌ－、Ｂｒ－、Ｉ－、ＣｌＯ４ －、ＢＦ４ －、ＣＨ３ＣＯＯ－、ＰＦ６ －等が挙げられる。　 In the general formula (VI), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R 25 —, —COO—R 26 — (provided that R 25 and R 26 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R 27 —O—R 28 —: R 27 and R 28 are each independently an alkylene group). -COO-R 26 -is preferable.
Examples of the counter anion M − include Cl − , Br − , I − , ClO 4 − , BF 4 − , CH 3 COO − , and PF 6 — .
　上記の如き特定の４級アンモニウム塩基を含有する部分構造は、１つのＡブロック中に２種以上含有されていてもよい。その場合、２種以上の４級アンモニウム塩基含有部分構造は、該Ａブロック中においてランダム共重合又はブロック共重合の何れの態様で含有されていてもよい。また、該４級アンモニウム塩基を含有しない部分構造が、Ａブロック中に含まれていてもよく、該部分構造の例としては、後述の（メタ）アクリル酸エステル系モノマー由来の部分構造等が挙げられる。　 The partial structure containing the specific quaternary ammonium base as described above may be contained in one or more A blocks. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done. *
　かかる４級アンモニウム塩基を含まない部分構造の、Ａブロック中の含有量は、好ましくは０～５０重量％、より好ましくは０～２０重量％であるが、かかる４級アンモニウム塩基非含有部分構造はＡブロック中に含まれないことが最も好ましい。　
　尚、上述するアクリル系ブロック共重合体のＡブロックは、４級化されていない未反応の３級アミノ基を有していてもよい。 The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, it is not included in the A block.
The A block of the acrylic block copolymer described above may have an unreacted tertiary amino group that has not been quaternized.
　Ａブロックがアミノ基を有する場合、アミノ基は１～３級のいずれでもよい。当該１～３級アミノ基を有する単量体の含有割合は、当該アクリル系ブロック共重合体を構成する単量体組成において、２０モル％以上であることが好適であり、より好ましくは５０モル％以上である。
　このアミノ基は、直接主鎖に結合していてもよいが、２価の連結基を介して主鎖に結合していてもよい。　 When the A block has an amino group, the amino group may be any one of primary to tertiary. The content ratio of the monomer having a primary to tertiary amino group is preferably 20 mol% or more, more preferably 50 mol in the monomer composition constituting the acrylic block copolymer. % Or more.
This amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.
　又、上記１～３級アミノ基としては、好ましくは－ＮＲ４１Ｒ４２（但し、Ｒ４１及びＲ４２は、それぞれ独立に、置換基を有していてもよい環状又は鎖状のアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を示す。）で表され、又、これを含む部分構造（繰返し単位）として好ましいものは、例えば下記一般式で表されるような構造が挙げられる。 The primary to tertiary amino group is preferably —NR 41 R 42 (wherein R 41 and R 42 are each independently a cyclic or chain alkyl group which may have a substituent, An aryl group which may have a substituent or an aralkyl group which may have a substituent is preferable. As a partial structure (repeating unit) containing this, preferred examples include A structure represented by the general formula can be given.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（但し、Ｒ４１及びＲ４２は、上記のＲ４１及びＲ４２と同義であり、Ｒ４３は炭素数１以上のアルキレン基、Ｒ４４は水素原子又はメチル基を示す。）
　中でも、Ｒ４１及びＲ４２はメチル基が好ましく、Ｒ４３はメチレン基、エチレン基が好ましく、Ｒ４４は水素原子もしくはメチル基であるのが好ましい。このような部分構造としては下記一般式で表されるジメチルアミノエチルアクリレートやジメチルアミノエチルメタアクリレート由来の構造等が、特に好適に用いられる。 (However, R 41 and R 42 have the same meanings as R 41 and R 42 described above, R 43 represents an alkylene group having 1 or more carbon atoms, and R 44 represents a hydrogen atom or a methyl group.)
Among them, R 41 and R 42 are preferably a methyl group, R 43 is preferably a methylene group or an ethylene group, and R 44 is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula is particularly preferably used.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（上記一般式中、Ｒ４４は前述と同義である。）
　更に、上記アミノ基を含有する部分構造は、１つのＡブロック中に２種以上含有されていてもよい。その場合、２種以上のアミノ基含有部分構造は、該Ａブロック中においてランダム共重合又はブロック共重合の何れの態様で含有されていてもよい。又、アミノ基を含有しない部分構造が、Ａブロック中に一部含まれていてもよく、そのような部分構造の例としては、（メタ）アクリル酸エステル系モノマー由来の部分構造等が挙げられる。係るアミノ基を含まない部分構造の、Ａブロック中の含有量は、好ましくは０～５０重量％、より好ましくは０～２０重量％であるが、係るアミノ基非含有部分構造はＡブロック中に含まれないことが最も好ましい。 (In the above general formula, R 44 has the same meaning as described above.)
Furthermore, the partial structure containing the said amino group may be contained 2 or more types in one A block. In that case, the two or more amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, a partial structure not containing an amino group may be partially contained in the A block, and examples of such a partial structure include a partial structure derived from a (meth) acrylate monomer. . The content of such a partial structure not containing an amino group in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably it is not included.
　Ａブロック中に４級アンモニウム塩基又はアミノ基のいずれか一方を有してもよく、両方を有してもよい。極性の低い溶媒に対して、４級アンモニウム塩基の溶解性は低く、アミノ基の溶解性は高い。そのため、レジスト中に極性の低い溶媒を多く使う場合には、分散剤のレジスト溶媒への溶解性を向上させる観点から、Ａブロック中に、４級アンモニウム塩基及びアミノ基を有するか、４級アンモニウム基を有さずアミノ基を有することが好ましく、４級アンモニウム基を有さずアミノ基を有することがより好ましい。
　一方、アクリル系ブロック共重合体を構成するＢブロックは、上述した４級アンモニウム塩基及びアミノ基を有さず、上述したＡブロックを構成するモノマーと共重合しうるモノマーから成るものであれば、特に制限は無い。Ｂブロックは、顔料吸着基となる窒素原子含有官能基を有さない親溶媒性の部位であり、溶媒に親和性があるため、分散剤に吸着した顔料を溶媒中に安定化させる働きがある。 The A block may have either one of a quaternary ammonium base or an amino group, or may have both. The solubility of a quaternary ammonium base is low and the solubility of an amino group is high in a solvent with low polarity. Therefore, when many solvents with low polarity are used in the resist, from the viewpoint of improving the solubility of the dispersant in the resist solvent, the A block has a quaternary ammonium base and an amino group or quaternary ammonium. It preferably has an amino group without a group, and more preferably has an amino group without a quaternary ammonium group.
On the other hand, the B block constituting the acrylic block copolymer has no quaternary ammonium base and amino group described above, and is composed of a monomer that can be copolymerized with the monomer constituting the A block described above. There is no particular limitation. The B block is a solvophilic site that does not have a nitrogen atom-containing functional group that serves as a pigment adsorbing group, and has an affinity for the solvent, and thus has a function of stabilizing the pigment adsorbed on the dispersant in the solvent. .
　Ｂブロックとしては、例えば、スチレン、α－メチルスチレンなどのスチレン系モノマー；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、グリシジル（メタ）アクリレート、ベンジル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、エチルアクリル酸グリシジル、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレートなどの（メタ）アクリル酸エステル系モノマー；（メタ）アクリル酸クロライドなどの（メタ）アクリル酸塩系モノマー；（メタ）アクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルアミノエチルアクリルアミドなどの（メタ）アクリルアミド系モノマー；酢酸ビニル；アクリロニトリル；アリルグリシジルエーテル、クロトン酸グリシジルエーテル；Ｎ－メタクリロイルモルホリン、などのコモノマーを共重合させたポリマー構造が挙げられる。　 Examples of the B block include styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic. Acid butyl, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, N, N-dimethylaminoethyl (Meth) acrylate monomers such as (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N , N- Vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether, (meth) acrylamide monomers such as methyl aminoethyl acrylamide N- methacryloyl morpholine, polymer structure obtained by copolymerizing comonomers such. *
　Ｂブロックとしては、特に下記式（ＶＩＩＩ）で表される、（メタ）アクリル酸エステル系モノマー由来の部分構造を含有するものが好ましい。　 As the B block, those containing a partial structure derived from a (meth) acrylic acid ester monomer represented by the following formula (VIII) are particularly preferable. *
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（上記式（ＶＩＩＩ）中、Ｒ４１は、水素原子又はメチル基を表す。Ｒ４２は、置換基を有していてもよい環状又は鎖状のアルキル基、置換基を有していてもよいアリル基、又は置換基を有していてもよいアラルキル基を表す。）　
　上記（メタ）アクリル酸エステル系モノマー由来の部分構造は、１つのＢブロック中に２種以上含有されていてもよい。もちろん該Ｂブロックは、更にこれら以外の部分構造を含有していてもよい。２種以上のモノマー由来の部分構造が、４級アンモニウム塩基を含有しないＢブロック中に存在する場合、各部分構造は該Ｂブロック中においてランダム共重合又はブロック共重合の何れの態様で含有されていてもよい。　 (In the above formula (VIII), R 41 represents a hydrogen atom or a methyl group. R 42 may have a cyclic or chain alkyl group which may have a substituent, or a substituent. Represents an allyl group or an aralkyl group which may have a substituent.)
Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
　Ｂブロック中に上記（メタ）アクリル酸エステル系モノマー由来の部分構造以外の部分構成を含有する場合、当該（メタ）アクリル酸エステル系モノマー以外の部分構造の、Ｂブロック中の含有量は、好ましくは０～９９重量％、より好ましくは０～８５重量％である。　
　本発明で用いるアクリル系分散剤は、このようなＡブロックとＢブロックとからなる、Ａ－Ｂブロック又はＢ－Ａ－Ｂブロック共重合型高分子化合物であるが、このようなブロック共重合体は、例えばリビング重合法にて調製される。　 When the B block contains a partial structure other than the partial structure derived from the (meth) acrylic acid ester monomer, the content of the partial structure other than the (meth) acrylic acid ester monomer in the B block is preferably Is from 0 to 99% by weight, more preferably from 0 to 85% by weight.
The acrylic dispersant used in the present invention is an AB block or BAB block copolymer type polymer compound composed of such an A block and a B block. Such a block copolymer Is prepared, for example, by a living polymerization method.
　リビング重合法にはアニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法がある。例えば、日本国特開２００７－２７０１４７号公報に記載の方法が挙げられる。
　尚、上記アクリル系ブロック共重合体のアミン価は、有効固形分換算で通常１～３００ｍｇＫＯＨ／ｇ程度であるが、その好ましい範囲は、Ａブロックが４級アンモニウム塩基を有する場合とそうでない場合とで異なる。なお、アミン価は、共重合体１ｇ中のアミノ基を中和するのに必要な酸のモル当量に対応したＫＯＨのｍｇ数で表した値である。 The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. For example, the method described in Japanese Patent Application Laid-Open No. 2007-270147 can be mentioned.
The amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferred range is when the A block has a quaternary ammonium base and when it does not. It is different. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of acid necessary for neutralizing the amino group in 1 g of the copolymer.
　即ち、本発明に係るＡ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体において、Ａブロックが４級アンモニウム塩基を有する場合、当該共重合体１ｇ中の４級アンモニウム塩基の量は、通常０．１～１０ｍｍｏｌであることが好ましく、この範囲外では、良好な耐熱性と分散性を兼備することができない場合がある。　
　なお、このようなブロック共重合体中には、通常、製造過程で生じたアミノ基が含有される場合があるが、そのアミン価は通常１～１００ｍｇＫＯＨ／ｇ程度、好ましくは１～８０ｍｇＫＯＨ／ｇ。より好ましくは１～５０ｍｇＫＯＨ／ｇである。 That is, in the AB block copolymer and the BAB block copolymer according to the present invention, when the A block has a quaternary ammonium base, the amount of the quaternary ammonium base in 1 g of the copolymer is Usually, it is preferably 0.1 to 10 mmol, and outside this range, it may not be possible to combine good heat resistance and dispersibility.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is usually about 1 to 100 mgKOH / g, preferably 1 to 80 mgKOH / g. . More preferably, it is 1 to 50 mgKOH / g.
　又、Ａブロックに４級アンモニウム塩基を含まない場合、当該共重合体のアミン価は、通常、５０～３００ｍｇＫＯＨ／ｇ程度、好ましくは５０～２００ｍｇＫＯＨ／ｇ、より好ましくは８０ｍｇＫＯＨ／ｇ以上１５０ｍｇＫＯＨ／ｇ以下、更に好ましくは９０～１５０ｍｇＫＯＨ／ｇである。
　このようなアクリル系ブロック共重合体の酸価は、該酸価の元となる酸性基の有無及び種類にもよるが、一般に低い方が好ましく、通常１００ｍｇＫＯＨ／ｇ以下であり、好ましくは５０ｍｇＫＯＨ／ｇ以下、より好ましくは４０ｍｇＫＯＨ／ｇ以下である。　 When the A block does not contain a quaternary ammonium base, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more and 150 mgKOH / g. Hereinafter, it is more preferably 90 to 150 mgKOH / g.
The acid value of such an acrylic block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably lower, usually 100 mgKOH / g or less, preferably 50 mgKOH / g. g or less, more preferably 40 mgKOH / g or less.
　また、アクリル系ブロック共重合体の分子量は、ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）では、通常１０００以上、１００，０００以下の範囲である。アクリル系ブロック共重合体の分子量が小さすぎると分散安定性が低下し、大きすぎると現像性、解像性が低下する傾向にある。　
　本発明においては、上述のものと同様の構造を有する市販のアクリル系ブロック共重合体を適用することもできる。　 The molecular weight of the acrylic block copolymer is usually in the range of 1000 or more and 100,000 or less in terms of polystyrene-reduced weight average molecular weight (Mw) measured by GPC. When the molecular weight of the acrylic block copolymer is too small, the dispersion stability decreases, and when it is too large, the developability and resolution tend to decrease.
In the present invention, a commercially available acrylic block copolymer having the same structure as described above can also be applied.
　本発明において、窒素原子を含有するアクリル系ブロック共重合体の含有量は、顔料に対して通常５重量％以上９０重量％以下であり、好ましくは５重量％以上６０重量％以下、更にこのましくは５重量％以上４０重量％以下である。窒素原子を含有するアクリル系ブロック共重合体の含有量が少な過ぎると、十分な分散性が得られない場合があり、多過ぎると相対的に他の成分の割合が減って電圧保持率が低下する一方、着色スペーサの形状、段差の形成ができない場合がある。 In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by weight or more and 90% by weight or less, preferably 5% by weight or more and 60% by weight or less based on the pigment. Or 5 to 40% by weight. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too much, the proportion of other components will decrease and the voltage holding ratio will decrease. On the other hand, the shape of the colored spacer and the formation of the step may not be possible.
　本発明においては、窒素原子を含有するアクリル系ブロック共重合体以外の分散剤を併用してもよい。併用する分散剤は、高分子分散剤であることが好ましく、着色剤とは全く構造の異なるポリマーであることが好ましい。
　併用する分散剤としては、例えば、ウレタン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤等を挙げることができる。 In the present invention, a dispersant other than an acrylic block copolymer containing a nitrogen atom may be used in combination. The dispersant used in combination is preferably a polymer dispersant, and is preferably a polymer having a completely different structure from the colorant.
Examples of the dispersant used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene diester-based dispersant, Examples thereof include polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
　本発明の着色感光性組成物は、着色剤の分散安定性の向上のために分散助剤を併用する事が好ましい。ここで分散助剤とは着色剤の分散性を高めるための顔料誘導体等をいう。
　顔料誘導体としてはアゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系等の誘導体が挙げられるが、中でもキノフタロン系が好ましい。顔料誘導体の置換基としてはスルホン酸基、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシル基、アミド基等が顔料骨格に直接又はアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよい。　 In the colored photosensitive composition of the present invention, it is preferable to use a dispersion aid together in order to improve the dispersion stability of the colorant. Here, the dispersion aid means a pigment derivative or the like for improving the dispersibility of the colorant.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Derivatives such as quinophthalone are preferable. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group directly on the pigment skeleton or an alkyl group, an aryl group, a complex Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
　顔料誘導体の具体例としてはフタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、ジオキサジンのスルホン酸誘導体等が挙げられる。　
　これらの顔料誘導体は１種を単独で或いは２種以上を組み合わせて用いることができる。　
　顔料誘導体を用いる場合、その使用量は顔料に対して通常０．１～３０重量％、好ましくは０．１～２０重量％以下、より好ましくは０．１～１０重量％、さらに好ましくは０．１～５重量％である。 Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
These pigment derivatives can be used alone or in combination of two or more.
When a pigment derivative is used, the amount used is usually from 0.1 to 30% by weight, preferably from 0.1 to 20% by weight, more preferably from 0.1 to 10% by weight, still more preferably from 0.1 to 30% by weight based on the pigment. 1 to 5% by weight.
　［２－７］その他の成分　
　本発明の遮光性感光性樹脂組成物には、上記の成分の他に、さらに重合加速剤、増感色素、界面活性剤、光酸発生剤、架橋剤、密着性向上剤、可塑剤、保存安定剤、表面保護剤、有機カルボン酸、有機カルボン酸無水物、現像改良剤、熱重合防止剤等を含んでいてもよい。　 [2-7] Other ingredients
In addition to the above components, the light-shielding photosensitive resin composition of the present invention further includes a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, and a storage. A stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic acid anhydride, a development improver, a thermal polymerization inhibitor and the like may be contained.
　［２－７－１］光酸発生剤
　光酸発生剤とは、紫外線により酸を発生することができる化合物であり、露光を行った際に発生する酸の作用により、例えばメラミン化合物等架橋剤があることで架橋反応を進行させることとなる。係る光酸発生剤の中でも、溶剤に対する溶解性、特に着色感光性組成物に使われる溶剤に対する溶解性が大きいものが好ましいものであり、例えば、ジフェニルヨードニウム、ジトリルヨードニウム、フェニル（ｐ－アニシル）ヨードニウム、ビス（ｍ－ニトロフェニル）ヨードニウム、ビス（ｐ－ｔｅｒｔ－ブチルフェニル）ヨードニウム、ビス（ｐ－クロロフェニル）ヨードニウム、ビス（ｎ－ドデシル）ヨードニウム、ｐ－イソブチルフェニル（ｐ－トリル）ヨードニウム、ｐ－イソプロピルフェニル（ｐ－トリル）ヨードニウムなどのジアリールヨードニウム、あるいはトリフェニルスルホニウムなどのトリアリールスルホニウムのクロリド、ブロミド、あるいはホウフッ化塩、ヘキサフルオロフォスフェート塩、ヘキサフルオロアルセネート塩、芳香族スルホン酸塩、テトラキス（ペンタフルオロフェニル）ボレート塩等や、ジフェニルフェナシルスルホニウム（ｎ－ブチル）トリフェニルボレート等のスルホニウム有機ホウ素錯体類、あるいは、２－メチル－４，６－ビストリクロロメチルトリアジン、２－（４－メトキシフェニル）－４，６－ビストリクロロメチルトリアジンなどのトリアジン化合物等を挙げることができるがこの限りではない。　 [2-7-1] Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays. By the action of the acid generated upon exposure, for example, a crosslinking agent such as a melamine compound. If there is, it will advance a crosslinking reaction. Among such photoacid generators, those having a high solubility in a solvent, particularly in a solvent used in a colored photosensitive composition, are preferable. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p Diaryl iodonium such as isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium chloride such as triphenylsulfonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoroa Senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts and the like, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Examples thereof include, but are not limited to, triazine compounds such as bistrichloromethyltriazine and 2- (4-methoxyphenyl) -4,6-bistrichloromethyltriazine.
　［２－７－２］架橋剤　
　本発明の着色感光性組成物には、さらに架橋剤を加えることができ、例えばメラミン又はグアナミン系の化合物を用いることができる。これら架橋剤としては、例えば、下記一般式（ＸＩ）で示されるメラミン又はグアナミン系の化合物を挙げることができる。　 [2-7-2] Crosslinking agent
A cross-linking agent can be further added to the colored photosensitive composition of the present invention, and for example, a melamine or guanamine compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XI).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（式中、Ｒ６１は－ＮＲ６６Ｒ６７基又はアリールを表し、Ｒ６１が－ＮＲ６６Ｒ６７基の場合はＲ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６及びＲ６７の一つ、そしてＲ６１がアリールの場合はＲ６２、Ｒ６３、Ｒ６４及びＲ６５の一つが－ＣＨ２ＯＲ６８基を表し、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６及びＲ６７の残りは互いに独立に、水素又は－ＣＨ２ＯＲ６８基を表し、ここでＲ６８は水素又はアルキルを表す。）　 (Wherein R 61 represents a —NR 66 R 67 group or aryl, and when R 61 is a —NR 66 R 67 group, one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 ) And when R 61 is aryl, one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group, and R 62 , R 63 , R 64 , R 65 , R 66 and R 67 The rest independently of one another represent hydrogen or a —CH 2 OR 68 group, where R 68 represents hydrogen or alkyl.)
　ここで、アリールは典型的にはフェニル、１－ナフチル又は２－ナフチルであり、これらのフェニルやナフチルには、アルキル、アルコキシ、ハロゲンなどの置換基が結合していてもよい。アルキル及びアルコキシは、それぞれ炭素数１～６程度であることができる。Ｒ６８で表されるアルキルは、上記のなかでも、メチル又はエチル、とりわけメチルであるのが一般的である。 Here, the aryl is typically phenyl, 1-naphthyl or 2-naphthyl, and a substituent such as alkyl, alkoxy or halogen may be bonded to the phenyl or naphthyl. Alkyl and alkoxy can each have about 1 to 6 carbon atoms. Among the above, alkyl represented by R 68 is generally methyl or ethyl, particularly methyl.
　一般式（ＸＩ）に相当するメラミン系化合物、すなわち下記一般式（ＸＩ－１）の化合物には、ヘキサメチロールメラミン、ペンタメチロールメラミン、テトラメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチルメラミン、テトラメトキシメチルメラミン、ヘキサエトキシメチルメラミンなどが包含される。　 Melamine compounds corresponding to the general formula (XI), that is, compounds of the following general formula (XI-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included. *
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６及びＲ６７の一つがアリールの場合はＲ６２、Ｒ６３、Ｒ６４及びＲ６５の一つが－ＣＨ２ＯＲ６８基を表し、Ｒ６２、Ｒ６３、Ｒ６４、Ｒ６５、Ｒ６６及びＲ６７の残りは互いに独立に、水素又は－ＣＨ２ＯＲ６８基を表し、ここにＲ６８は水素又はアルキルを表す。）　 (In the formula, when one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is aryl, one of R 62 , R 63 , R 64 and R 65 represents a —CH 2 OR 68 group. , R 62 , R 63 , R 64 , R 65 , R 66 and the rest of R 67 independently of one another represent hydrogen or a —CH 2 OR 68 group, where R 68 represents hydrogen or alkyl.)
　また、一般式（ＸＩ）に相当するグアナミン系化合物、すなわち一般式（ＸＩ）中のＲ６１がアリールである化合物には、テトラメチロールベンゾグアナミン、テトラメトキシメチルベンゾグアナミン、トリメトキシメチルベンゾグアナミン、テトラエトキシメチルベンゾグアナミンなどが包含される。 Further, guanamine compounds corresponding to the general formula (XI), that is, compounds in which R 61 in the general formula (XI) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.
　さらに、メチロール基又はメチロールアルキルエーテル基を有する架橋剤を用いることもできる。以下にその例を挙げる。　
　２，６－ビス（ヒドロキシメチル）－４－メチルフェノール、４－ｔｅｒｔ－ブチル－２，６－ビス（ヒドロキシメチル）フェノール、５－エチル－１，３－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－トリアジン－２－オン（通称Ｎ－エチルジメチロールトリアゾン）又はそのジメチルエーテル体、ジメチロールトリメチレン尿素又はそのジメチルエーテル体、３，５－ビス（ヒドロキシメチル）ペルヒドロ－１，３，５－オキサジアジン－４－オン（通称ジメチロールウロン）又はそのジメチルエーテル体、テトラメチロールグリオキザールジウレイン又はそのテトラメチルエーテル体。　
　尚、これら架橋剤は１種を単独で用いても、２種以上を組み合わせて使用してもよい。　架橋剤を用いる際の量は、遮光性感光性樹脂組成物の全固形分に対して０．１～１５重量％が好ましく、特に好ましくは０．５～１０重量％である。　 Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. Examples are given below.
2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 , 5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (commonly called dimethyloluron) or a dimethyl ether thereof, tetramethylol glyoxal diurein or a tetramethyl ether thereof.
In addition, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. The amount when the crosslinking agent is used is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the light-shielding photosensitive resin composition.
　［２－７－３］密着向上剤
　本発明の遮光性感光性樹脂組成物には細い線やドットを充分密着させるために、密着向上剤を含有させてもよい。　
　密着向上剤としては、窒素原子を含有する化合物や燐酸基含有化合物、シランカップリング剤などが好ましく、窒素原子を含有する化合物としては、例えば、ジアミン類（日本国特開平１１－１８４０８０号公報記載の密着増強剤、他）やアゾール類が好ましい。なかでもアゾール類が好ましく、特にイミダゾール類（日本国特開平９－２３６９２３号公報記載の密着向上剤、他）、ベンゾイミダゾール類、ベンゾトリアゾール類（日本国特開２０００－１７１９６８号公報記載の密着向上剤、他）が好ましく、イミダゾール類とベンゾイミダゾール類が最も好ましい。これらのなかで、カブリが生じにくく、密着性を大きく向上させることができる点から２－ヒドロキシベンゾイミダゾール、２－ヒドロキシエチルベンゾイミダゾール、ベンゾイミダゾール、２－ヒドロキシイミダゾール、イミダゾール、２－メルカプトイミダゾール、２－アミノイミダゾールが好ましく、２－ヒドロキシベンゾイミダゾール、ベンゾイミダゾール、２－ヒドロキシイミダゾール、イミダゾールが特に好ましい。シランカップリング剤の種類としては、エポキシ系、メタクリル系、アミノ系等種々の物が使用できるが、特にエポキシ系のシランカップリング剤が好ましい。　 [2-7-3] Adhesion improver The light-shielding photosensitive resin composition of the present invention may contain an adhesion improver in order to sufficiently adhere fine lines and dots.
As the adhesion improver, a compound containing a nitrogen atom, a phosphoric acid group-containing compound, a silane coupling agent or the like is preferable. Examples of the compound containing a nitrogen atom include diamines (described in Japanese Patent Application Laid-Open No. 11-184080). And other azoles are preferred. Among them, azoles are preferable, and in particular, imidazoles (adhesion improvers described in JP-A-9-236923, etc.), benzimidazoles, benzotriazoles (adhesion improvement described in JP-A-2000-171968). Agents, etc.), and imidazoles and benzimidazoles are most preferred. Of these, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2 are less likely to cause fogging and greatly improve adhesion. -Aminoimidazole is preferred, with 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole and imidazole being particularly preferred. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.
　これらは１種を単独で或いは２種以上を組み合わせて用いることができる。　
　これらの密着向上剤を配合する場合、その配合割合は、用いる密着向上剤の種類によっても異なるが、着色感光性組成物の全固形分に対して０．０１～５重量％、特に０．０５～３重量％とすることが好ましい。これよりも少ないと十分な密着性の向上効果が得られない場合があり、多すぎると現像性を下げる場合がある。　 These can be used alone or in combination of two or more.
When blending these adhesion improvers, the blending ratio varies depending on the type of adhesion improver used, but is 0.01 to 5% by weight, particularly 0.05%, based on the total solid content of the colored photosensitive composition. It is preferable to set it to 3% by weight. If it is less than this, sufficient adhesion improving effect may not be obtained, and if it is too much, developability may be lowered.
　［２－７－４］増感色素　
　増感色素としては、例えば日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。　 [2-7-4] Sensitizing dye
Examples of the sensitizing dye include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335. Coumarin dyes having a heterocyclic ring described in JP-A No. 3-239703, 3-ketocoumarin compounds described in JP-A No. 3-239703, JP-A No. 5-289335, JP-A No. 6-19240 Pyrromethene dyes, etc., Japanese Patent Application Publication No. 47-2528, Japanese Patent Application Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Application Publication No. 48-84183, Japan JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56 No. 03, Japanese Laid-Open Patent Publication No. 2-69, Japanese Laid-Open Patent Publication No. 57-168088, Japanese Laid-Open Patent Publication No. 5-107761, Japanese Laid-Open Patent Publication No. 5-210240, Japanese Laid-Open Patent Publication No. 4-4. Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-288818.
　これらは１種を単独で或いは２種以上を組み合わせて用いることができる。　
　増感色素を配合する場合、着色感光性組成物中の全固形分中における増感色素の含有率は、通常０．０１～５重量％、好ましくは０．０５～３重量％である。これより少ないと増感効果が出ない場合があり、多すぎると現像性を下げる場合がある。　 These can be used alone or in combination of two or more.
When a sensitizing dye is blended, the content of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, the sensitization effect may not be obtained, and if it is too much, the developability may be lowered.
　［２－７－５］界面活性剤　
　界面活性剤としてはアニオン系、カチオン系、非イオン系、両性界面活性剤等各種のものの１種又は２種以上を用いることができるが、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤を用いるのが好ましい。また、フッ素系やシリコン系のものは、塗布性の面で効果的である。　
　界面活性剤の配合割合としては、着色感光性組成物中の全固形分に対して通常０．００１～１０重量％、好ましくは０．００５～１重量％、さらに好ましくは０．０１～０．５重量％、最も好ましくは０．０３～０．３重量％の範囲である。界面活性剤の添加量が上記範囲よりも少ないと塗布膜の平滑性、均一性が発現できない場合があり、多いと塗布膜の平滑性、均一性が発現できない場合がある他、他の特性が悪化する場合がある。　 [2-7-5] Surfactant
As the surfactant, one or more of various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. It is preferable to use an ionic surfactant. In addition, fluorine-based and silicon-based materials are effective in terms of coating properties.
The blending ratio of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0. 0% by weight with respect to the total solid content in the colored photosensitive composition. It is in the range of 5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the addition amount is large, the smoothness and uniformity of the coating film may not be expressed, and other characteristics may be exhibited. It may get worse.
　［２－７－６］有機カルボン酸、有機カルボン酸無水物
　本発明の着色感光性組成物は、現像性の向上や地汚れ改善の目的で有機カルボン酸及び有機カルボン酸無水物のうち少なくとも一方を含んでいてもよい。　
　有機カルボン酸としては、脂肪族カルボン酸及び芳香族カルボン酸のうち少なくとも一方が挙げられる。　 [2-7-6] Organic Carboxylic Acid, Organic Carboxylic Anhydride The colored photosensitive composition of the present invention is at least one of an organic carboxylic acid and an organic carboxylic anhydride for the purpose of improving developability and improving background stains. May be included.
Examples of the organic carboxylic acid include at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid.
　脂肪族カルボン酸としては、具体的には、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸、グリコール酸、アクリル酸、メタクリル酸などのモノカルボン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シクロヘキサンジカルボン酸、シクロヘキセンジカルボン酸、イタコン酸、シトラコン酸、マレイン酸、フマル酸などのジカルボン酸、トリカルバリル酸、アコニット酸、カンホロン酸などのトリカルボン酸などが挙げられる。また、芳香族カルボン酸としては、具体的には、安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸、フタル酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、メロファン酸、ピロメリット酸、フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸などのフェニル基に直接カルボキシル基が結合したカルボン酸、及びフェニル基から炭素結合を介してカルボキシル基が結合したカルボン酸等が挙げられる。　 Specific examples of the aliphatic carboxylic acid include monoacids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethyl Examples thereof include dicarboxylic acids such as succinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and fumaric acid, and tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoric acid. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and merophanic acid. , Pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, umbelic acid, etc. Examples thereof include a carboxylic acid in which a carboxyl group is directly bonded to a group, and a carboxylic acid in which a carboxyl group is bonded from a phenyl group through a carbon bond. *
　上記有機カルボン酸の中では、モノカルボン酸、ジカルボン酸が好ましく、中でもマロン酸、グルタル酸、グリコール酸が更に好ましく、マロン酸が特に好ましい。　
　上記有機カルボン酸の分子量は、通常１０００以下であり、通常５０以上である。上記有機カルボン酸の分子量が大きすぎると地汚れ改善効果が不十分となる場合があり、少なすぎると昇華、揮発などにより、添加量の減少やプロセス汚染を起こす恐れがある。　 Among the above organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and among them, malonic acid, glutaric acid, and glycolic acid are more preferable, and malonic acid is particularly preferable.
The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving background stains may be insufficient.
　有機カルボン酸無水物としては、脂肪族カルボン酸無水物及び芳香族カルボン酸無水物のうち少なくとも一方が挙げられ、脂肪族カルボン酸無水物としては、具体的には無水酢酸、無水トリクロロ酢酸、無水トリフルオロ酢酸、無水テトラヒドロフタル酸、無水コハク酸、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水グルタル酸、無水１，２－シクロヘキセンジカルボン酸、無水ｎ－オクタデシルコハク酸、無水５－ノルボルネン－２，３－ジカルボン酸などの脂肪族カルボン酸無水物が挙げられる。芳香族カルボン酸無水物としては、具体的には無水フタル酸、トリメリット酸無水物、ピロメリット酸無水物、無水ナフタル酸などが挙げられる。　 Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, and anhydrous Trifluoroacetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene anhydride Examples thereof include aliphatic carboxylic acid anhydrides such as 2,3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. *
　上記有機カルボン酸無水物の中では、無水マレイン酸、無水コハク酸、無水イタコン酸、無水シトラコン酸が好ましく、無水マレイン酸が更に好ましい。　
　上記有機カルボン酸無水物の分子量は、通常８００以下、好ましくは６００以下、更に好ましくは５００以下であり、通常５０以上である。上記有機カルボン酸無水物の分子量が大きすぎると地汚れ改善効果が不十分となる場合があり、少なすぎると昇華、揮発などにより、添加量の減少やプロセス汚染を起こす恐れがある。　 Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving background stains may be insufficient.
　これらの有機カルボン酸及び有機カルボン酸無水物は、それぞれ１種を単独で用いてもよく、２種以上を混合して用いてもよい。　
　これらの有機カルボン酸及び有機カルボン酸無水物の添加量は、それぞれ、本発明の遮光性感光性樹脂組成物の全固形分中、通常０．０１重量％～５重量％、好ましくは０．０３重量％～３重量％である。その添加量が少なすぎると十分な添加効果が得られない場合があり、多すぎると表面平滑性や感度が悪化し、未溶解剥離片が発生する場合がある。　 One of these organic carboxylic acids and organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.
The addition amount of these organic carboxylic acid and organic carboxylic acid anhydride is usually 0.01% by weight to 5% by weight, preferably 0.03% in the total solid content of the light-shielding photosensitive resin composition of the present invention. % By weight to 3% by weight. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and undissolved peeling pieces may be generated.
　［２－７－７］熱重合防止剤　
　熱重合防止剤としては、例えば、ハイドロキノン、ｐ－メトキシフェノール、ピロガロール、カテコール、２，６－ｔ－ブチル－ｐ－クレゾール、β－ナフトール等の１種又は２種以上が用いられる。　
　熱重合防止剤の配合割合は、遮光性感光性樹脂組成物中の全固形分に対し０～２重量％の範囲であることが好ましく、これよりも多いと遮光性、感光性樹脂組成物の感度を低下させる場合がある。　 [2-7-7] Thermal polymerization inhibitor
As the thermal polymerization inhibitor, for example, one or more of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used.
The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight based on the total solid content in the light-shielding photosensitive resin composition. Sensitivity may be reduced.
　［２－７－８］可塑剤　
　可塑剤としては、例えば、ジオクチルフタレート、ジドデシルフタレート、トリエチレングリコールジカプリレート、ジメチルグリコールフタレート、トリクレジルホスフェート、ジオクチルアジペート、ジブチルセバケート、トリアセチルグリセリン等の１種又は２種以上が用いられる。　
　これら可塑剤の配合割合は、遮光性感光性樹脂組成物中の全固形分に対し５重量％以下の範囲であることが好ましく、これよりも多いと樹脂ブラックマトリックスの硬化点が低下する。　 [2-7-8] Plasticizer
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. It is done.
The blending ratio of these plasticizers is preferably in the range of 5% by weight or less with respect to the total solid content in the light-shielding photosensitive resin composition.
　［３］着色感光性組成物の製造方法　
　次に本発明の着色感光性組成物の製造方法について説明する。　
　以下、着色剤として顔料を使った着色感光性組成物について説明する。
　まず（ａ）顔料と（ｆ）分散剤および必要な成分を用い、顔料分散液を製造する。次に、上述得られた顔料分散液、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、及び（ｅ）溶剤を混合して着色感光性組成物はを製造する。必要に応じて、前述の他の成分を混合してもよい。 [3] Method for producing colored photosensitive composition
Next, the manufacturing method of the coloring photosensitive composition of this invention is demonstrated.
Hereinafter, a colored photosensitive composition using a pigment as a colorant will be described.
First, a pigment dispersion is produced using (a) a pigment, (f) a dispersant and necessary components. Next, the pigment dispersion obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent are mixed to give a colored photosensitive composition. Manufacturing. You may mix the other above-mentioned component as needed.
　［３－１］（ａ）顔料分散液の製造方法　
　本発明に係る顔料分散液の製造方法としては種々の方法を採用することができる。以下にその一例を示す。　
　まず、顔料、溶剤、及び分散剤／分散助剤を各々所定量秤量し、分散処理工程において、顔料を分散させて液状の顔料分散液とする。顔料、溶剤、及び分散剤／分散助剤としては、前述の着色感光性組成物の構成成分として記載されたものが使用できる。 [3-1] (a) Method for producing pigment dispersion
Various methods can be adopted as a method for producing the pigment dispersion according to the present invention. An example is shown below.
First, a predetermined amount of each of the pigment, the solvent, and the dispersant / dispersion aid is weighed, and in the dispersion treatment step, the pigment is dispersed to obtain a liquid pigment dispersion. As the pigment, the solvent, and the dispersant / dispersion aid, those described as the constituent components of the above-mentioned colored photosensitive composition can be used.
　この分散処理工程では、ペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザーなどを使用することができる。サンドグラインダーを用いて分散処理を行う場合は、０．１～数ｍｍ径のガラスビーズ、又はジルコニアビーズを用いるのが好ましい。　
　この分散処理を行うことによって顔料が微粒子化されるため、この顔料分散液を用いた着色感光性組成物は塗布特性および直線性などの製版性能が向上する。　 In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm.
Since the pigment is finely divided by this dispersion treatment, the colored photosensitive composition using the pigment dispersion is improved in plate making performance such as coating characteristics and linearity.
　顔料を分散処理する際には、前記のアルカリ可溶性樹脂などを適宜併用してもよい。　
　分散処理する際の温度は通常０℃～１００℃の範囲、好ましくは室温～８０℃の範囲に設定する。なお、分散時間は、顔料分散液の組成（顔料、溶剤、分散剤／分散助剤等）、及びサンドグラインダーの装置の大きさなどにより適正時間が異なるため、適宜調整する必要がある。 When dispersing the pigment, the alkali-soluble resin or the like may be used in combination as appropriate.
The temperature during the dispersion treatment is usually set in the range of 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The appropriate dispersion time depends on the composition of the pigment dispersion (pigment, solvent, dispersant / dispersion aid, etc.), the size of the sand grinder apparatus, and the like.
　顔料分散液中の（ａ）顔料の含有量は、通常５重量％以上５０重量％以下であり、好ましくは１０重量％以上４０重量％以下である。
　顔料分散液中の（ｆ）分散剤の含有量は、顔料に対して通常５重量％以上９０重量％以下であり、好ましくは５重量％以上６０重量％以下、更にこのましくは５重量％以上４０重量以下である。 The content of the pigment (a) in the pigment dispersion is usually 5% by weight to 50% by weight, and preferably 10% by weight to 40% by weight.
The content of the dispersant (f) in the pigment dispersion is usually 5% by weight to 90% by weight, preferably 5% by weight to 60% by weight, more preferably 5% by weight, based on the pigment. It is 40 weight or less.
　顔料分散液中の分散助剤の含有量は、顔料に対して通常０．１～３０重量％、好ましくは０．１～２０重量％以下、より好ましくは０．１～１０重量％、さらに好ましくは０．１～５重量％である。
　顔料分散液中のアルカリ可溶性樹脂（ｂ）の含有量は、顔料に対して通常０重量％以上１００重量％以下であり、好ましくは５重量％以上８０重量％以下、更にこのましくは５重量％以上６０重量％以下である。 The content of the dispersion aid in the pigment dispersion is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, still more preferably based on the pigment. Is 0.1 to 5% by weight.
The content of the alkali-soluble resin (b) in the pigment dispersion is usually 0 to 100% by weight, preferably 5 to 80% by weight, more preferably 5% by weight based on the pigment. % To 60% by weight.
　［３－２］着色感光性組成物の製造方法　
　次に上記分散処理により得られた顔料分散液（インキ）と着色感光性組成物成分として必要な前記の他の分を添加、攪拌混合して均一な着色感光性組成物溶液とする。この製造工程においては微細なゴミが液中に混じることが多いため、得られた着色感光性組成物溶液はフィルター等により濾過処理するのが望ましい。　
　尚、着色剤として顔料以外（例えば染料）を使った着色感光性組成物は、公知の方法で製造できる。 [3-2] Method for producing colored photosensitive composition
Next, the pigment dispersion (ink) obtained by the above dispersion treatment and the above-mentioned other components necessary as a colored photosensitive composition component are added and mixed with stirring to obtain a uniform colored photosensitive composition solution. In this manufacturing process, fine dust is often mixed in the liquid. Therefore, it is desirable to filter the obtained colored photosensitive composition solution with a filter or the like.
In addition, the coloring photosensitive composition using other than a pigment (for example, dye) as a coloring agent can be manufactured by a well-known method.
　［４］着色スペーサの形成方法
　本実施の形態の着色感光性組成物は、公知のカラーフィルター用着色感光性組成物と同様の方法により使用されるが、以下、着色スペーサとして使用される場合について説明する。　
　通常、着色スペーサが設けられるべき基板上に、着色感光性組成物溶液を、塗布等の方法により膜状或いはパターン状に供給し、溶剤を乾燥させる。続いて、露光－現像を行うフォトリソグラフィー法によりパターン形成を行う。その後、必要により追露光や熱硬化処理を行うことにより、該基板上に着色スペーサが形成される。 [4] Method for Forming Colored Spacer The colored photosensitive composition of the present embodiment is used in the same manner as a known colored photosensitive composition for a color filter. explain.
Usually, a colored photosensitive composition solution is supplied into a film or pattern by a method such as coating on a substrate on which a colored spacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a photolithography method in which exposure and development are performed. Then, if necessary, a colored spacer is formed on the substrate by performing additional exposure or thermosetting treatment.
　［４－１］基板への供給方法　
　本実施の形態の着色感光性組成物は、通常、溶剤に溶解或いは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法などによって行うことができる。中でも、ダイコート法によれば、塗布液の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くない、異物発生が抑制されるなど、総合的な観点から好ましい。　 [4-1] Supplying method to substrate
The colored photosensitive composition of the present embodiment is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. As the supply method, 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. Above all, according to the die coating method, the usage amount of the coating liquid is greatly reduced, and there is no influence of mist adhering when the spin coating method is used. It is preferable from the viewpoint.
　塗布量は用途により異なるが、例えば着色スペーサの場合には、乾燥膜厚として、通常、０．５μｍ～１０μｍ、好ましくは１μｍ～９μｍ、特に好ましくは１μｍ～７μｍの範囲である。また、乾燥膜厚あるいは最終的に形成された着色スペーサの高さが、基板全域に渡って均一であることが重要である。ばらつきが大きい場合には、液晶パネルにムラ欠陥を生ずることとなる。また、インクジェット法や印刷法などにより、パターン状に供給されても良い。　
　尚、基板としてはガラス基板など、公知の基板を使用することができる。また、基板表面は平面であることが好適である。　 The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. Further, it is important that the dry film thickness or the height of the finally formed colored spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an ink jet method or a printing method.
A known substrate such as a glass substrate can be used as the substrate. The substrate surface is preferably a flat surface.
　［４－２］乾燥方法　
　基板上に着色感光性組成物溶液を供給した後の乾燥は、ホットプレート、ＩＲオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。また、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせても良い。　
　　乾燥の条件は、溶剤成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。乾燥時間は、溶剤成分の種類、使用する乾燥機の性能などに応じて、通常は、４０℃～１３０℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０℃～１１０℃の温度で３０秒～３分間の範囲で選ばれる。　 [4-2] Drying method
Drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, IR oven, or 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, the performance of the dryer used, and the like. 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.
　［４－３］露光方法　
　露光は、着色感光性組成物の塗布膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを着色感光性組成物の塗布膜に近接させる方法や、露光マスクを着色感光性組成物の塗布膜から離れた位置に配置し、該露光マスクを介した露光光を投影する方法によっても良い。また、マスクパターンを用いないレーザー光による走査露光方式によっても良い。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ったりしてもよい。　 [4-3] Exposure method
The exposure is performed by superimposing a negative mask pattern on the coating film of the colored photosensitive composition and irradiating an ultraviolet or visible light source through the mask pattern. When exposure is performed using an exposure mask, the exposure mask is placed close to the coating film of the colored photosensitive composition, or the exposure mask is placed at a position away from the coating film of the colored photosensitive composition, and the exposure is performed. 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. At this time, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure is performed after the formation of an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer or in a deoxygenated atmosphere. Or you may.
　上記の露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプなどのランプ光源や、アルゴンイオンレーザー、ＹＡＧレーザー、エキシマレーザー、窒素レーザー、ヘリウムカドミニウムレーザー、青紫色半導体レーザー、近赤外半導体レーザーなどのレーザー光源などが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルタを利用することもできる。　 The light source used for the above exposure is not particularly limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include 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 used by irradiating light of a specific wavelength. *
　光学フィルタとしては、例えば薄膜で露光波長における光透過率を制御可能なタイプでも良く、その場合の材質としては、例えばＣｒ化合物（Ｃｒの酸化物、窒化物、酸窒化物、フッ化物など）、ＭｏＳｉ、Ｓｉ、Ｗ、Ａｌ等が挙げられる。　
　また、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する為の方法においては、露光マスクとして、光の透過を遮る遮光層と光を透過させる開口部とを有し、一部の開口部の平均光透過率が他の開口部の平均光透過率より小さい露光マスクを用いる方法、即ち遮光層（光透過率０％）と複数の開口部を有し、平均光透過率の最も高い開口部（通常、光透過率１００％。以下完全透過開口部という）に対して平均光透過率の小さい開口部（中間透過開口部）を有する露光マスクを用いる方法を利用することができる。　 As the optical filter, for example, a thin film type that can control the light transmittance at the exposure wavelength may be used, and as a material in that case, for example, Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), MoSi, Si, W, Al, etc. are mentioned.
Further, in the method for forming colored spacers having different heights by photolithography, the exposure mask includes a light shielding layer that blocks light transmission and an opening portion that transmits light, and a part of the opening portions. Using an exposure mask whose average light transmittance is smaller than the average light transmittance of other openings, that is, an opening having a light shielding layer (light transmittance 0%) and a plurality of openings, and having the highest average light transmittance A method using an exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a portion (usually 100% light transmission, hereinafter referred to as a complete transmission opening) can be used.
　中間透過開口部の形成方法としては、上記の光学フィルタをマスクパターンの開口部（透光部）に任意に配置した、即ち光学フィルタを設けた開口部（中間透過開口部）と設けていない開口部（完全透過開口部）を適宜配置したマスクを用いる方法をとることができる。これにより、一回の露光工程により開口部の透光率に応じた光重合率の異なるパターンを形成することが可能となり、例えば一回の露光工程で高さの異なるパターンを同時に一括形成することが可能となる。　 As a method for forming the intermediate transmission opening, the above optical filter is arbitrarily arranged in the opening (translucent part) of the mask pattern, that is, the opening provided with the optical filter (intermediate transmission opening) and the opening not provided. A method using a mask in which portions (completely transmissive openings) are appropriately arranged can be employed. This makes it possible to form patterns with different photopolymerization rates in accordance with the light transmittance of the openings by a single exposure process, for example, simultaneously forming patterns having different heights in a single exposure process. Is possible. *
　また、もう一つ他の中間透過開口部の形成方法としては、日本国特開２００３－３４４８６０号公報に記載されている、遮光部と完全透過部を微小なマトリックスパターン状や微細なスリットパターン状に配置することにより、平均光透過率を調整した（完全透過開口部に対して光透過率の小さい）中間透過開口部を有する露光マスクを形成することも出来る。
　本実施の形態における露光量としては、通常、１ｍＪ／ｃｍ２以上、好ましくは５ｍＪ／ｃｍ２以上、より好ましくは１０ｍＪ／ｃｍ２以上であり、通常３００ｍＪ／ｃｍ２以下、好ましくは２００ｍＪ／ｃｍ２以下、より好ましくは１５０ｍＪ／ｃｍ２以下である。　
　また、近接露光方式の場合には、露光対象とマスクパターンとの距離としては、通常１０μｍ以上、好ましくは５０μｍ以上、より好ましくは７５μｍ以上であり、通常５００μｍ以下、好ましくは４００μｍ以下、より好ましくは３００μｍ以下である。 As another method for forming the intermediate transmission opening, as described in Japanese Patent Application Laid-Open No. 2003-344860, the light shielding portion and the complete transmission portion are formed in a fine matrix pattern shape or a fine slit pattern shape. The exposure mask having an intermediate transmission opening whose average light transmittance is adjusted (the light transmission is smaller than that of the complete transmission opening) can be formed.
The exposure amount in the present embodiment, usually, 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 Hereinafter, it is more preferably 150 mJ / cm 2 or less.
In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.
　［４－４］現像方法　
　上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。この水溶液には、さらに界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。　 [4-4] Development method
After performing the above exposure, 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.
　アルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－・ジ－又はトリエタノールアミン、モノ－・ジ－又はトリメチルアミン、モノ－・ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－・ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、２種以上の混合物であってもよい。　 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. *
　上記界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤；アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤；アルキルベタイン類、アミノ酸類などの両性界面活性剤、が挙げられる。　 Examples of the surfactant 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. *
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールなどが挙げられる。有機溶剤は、単独でも水溶液と併用して使用できる。　
　現像処理の方法については特に制限は無いが、通常、１０℃～５０℃、好ましくは１５℃～４５℃の現像温度で、浸漬現像、スプレー現像、ブラシ現像、超音波現像等の方法により行われる。　 Examples of the organic solvent 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 method is not particularly limited, but is usually performed at a development temperature of 10 ° C. to 50 ° C., preferably 15 ° C. to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. .
　［４－５］追露光及び熱硬化処理　
　現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行っても良く、また熱硬化処理を行っても良い。この際の熱硬化処理条件は、温度は１００℃～２８０℃の範囲、好ましくは１５０℃～２５０℃の範囲で選ばれ、時間は５分間～６０分間の範囲で選ばれる。　 [4-5] Additional exposure and thermosetting treatment
If necessary, the substrate after development may be subjected to additional exposure by a method similar to the above exposure method, or may be subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is selected 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.
　本実施の形態の着色感光性組成物は、液晶ディスプレイ等のカラーフィルター等において、ブラックマトリクス、オーバーコート、リブ及び着色スペーサ等を形成する際に好適に用いられる着色感光性組成物である。また特にフォトリソグラフィー法により特に高さの異なる着色スペーサを同時に形成する為の方法に適した着色感光性組成物を提供することが出来る。また本実施の形態によれば、高品質なカラーフィルターや液晶表示装置等を提供することができる。 The colored photosensitive composition of the present embodiment is a colored photosensitive composition that is suitably used when forming a black matrix, an overcoat, a rib, a colored spacer, and the like in a color filter such as a liquid crystal display. In particular, a colored photosensitive composition suitable for a method for simultaneously forming colored spacers having different heights by a photolithography method can be provided. In addition, according to this embodiment, a high-quality color filter, a liquid crystal display device, and the like can be provided.
　［５］着色スペーサ　
　本発明の着色感光性組成物により形成された着色スペーサは、略円柱状スペーサパターンが好ましい。
　完全透過開口部の着色スペーサパターンの下断面径は、通常１５μｍ超過４５μｍ未満であり、好ましくは１８μｍ超過４０μｍ未満である。この範囲より低い場合、圧縮特性が悪くなる傾向があり、この範囲より高い場合、基板上の面積が増えるためパネル構造上には好ましくない。 [5] Colored spacer
The colored spacer formed from the colored photosensitive composition of the present invention preferably has a substantially cylindrical spacer pattern.
The lower cross-sectional diameter of the colored spacer pattern of the complete transmission opening is usually more than 15 μm and less than 45 μm, preferably more than 18 μm and less than 40 μm. If it is lower than this range, the compression characteristics tend to be poor, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.
　中間透過開口部の着色スペーサパターンの下断面径は、通常２０μｍ超過５０μｍ未満であり、好ましくは３０μｍ超過４０μｍ未満である。この範囲より低い場合、圧縮特性が悪くなる傾向があり、この範囲より高い場合、基板上の面積が増えるためパネル構造上には好ましくない。
　完全透過開口部の着色スペーサパターンの高さと中間透過開口部の着色スペーサパターンの高さの差異（ΔＨ）は、完全透過開口部の着色スペーサパターンの高さが２．８μｍ超過３．２μｍ未満の場合、通常０．２５μｍ以上１．０μｍ以下であり、好ましくは０．３５μｍ超過０．８０μｍ以下であり、より好ましくは０．４μｍ超過０．６μｍ以下である。この範囲より低い場合、耐荷重性が悪くなる傾向があり、この範囲より高い場合、圧縮限界を超える傾向がある。 The lower cross-sectional diameter of the colored spacer pattern of the intermediate transmission opening is usually more than 20 μm and less than 50 μm, preferably more than 30 μm and less than 40 μm. If it is lower than this range, the compression characteristics tend to be poor, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.
The difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is that the height of the colored spacer pattern in the completely transmissive opening exceeds 2.8 μm and less than 3.2 μm. In this case, it is usually 0.25 μm or more and 1.0 μm or less, preferably 0.35 μm or more and 0.80 μm or less, more preferably 0.4 μm or more and 0.6 μm or less. When it is lower than this range, the load resistance tends to deteriorate, and when it is higher than this range, the compression limit tends to be exceeded.
　［６］カラーフィルター
　本発明のカラーフィルターは、上述のような本発明の着色スペーサを備えるものであり、例えば透明基板としてのガラス基板上に、ブラックマトリクスと、赤色、緑色、青色の画素着色層と、オーバーコート層とが積層されて、着色スペーサを形成した後配向膜を形成して製造される。配向膜としては、ポリイミド等の樹脂膜が好適である。 [6] Color filter The color filter of the present invention includes the above-described colored spacer of the present invention. For example, a black matrix and red, green, and blue pixel coloring layers on a glass substrate as a transparent substrate. And an overcoat layer are laminated to form a colored spacer, and then an alignment film is formed. As the alignment film, a resin film such as polyimide is suitable.
　［７］液晶表示装置
　本発明の液晶表示装置は上述のような本発明の着色スペーサを有するカラーフィルター備えるものであり、例えば、上述のようなカラーフィルターと液晶駆動側基板を貼り合わせて液晶セルを形成する。形成した液晶セルに液晶を注入して製造される。 [7] Liquid crystal display device The liquid crystal display device of the present invention is provided with a color filter having the colored spacer of the present invention as described above. For example, a liquid crystal cell is formed by laminating the above color filter and a liquid crystal driving side substrate. Form. Manufactured by injecting liquid crystal into the formed liquid crystal cell.
　次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本実施の形態はその要旨を超えない限り、以下の実施例に限定されるものではない。
　以下の実施例及び比較例で用いた着色感光性組成物の構成成分は次の通りである。　
　なお、以下において「部」は「重量部」を表す。 Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.
The components of the colored photosensitive composition used in the following examples and comparative examples are as follows.
In the following, “part” represents “part by weight”.
　＜アルカリ可溶性樹脂－１＞　
　新中村化学工業（株）製　「ＡＤＥＰ０２」（（ＭＷ＝３５００～４５００、酸価＝約１１０ｍｇ－ＫＯＨ／ｇ、アルカリ可溶性樹脂（Ａ－２）に該当）　
　＜アルカリ可溶性樹脂－２＞　
　日本化薬（株）製「ＺＣＲ－１６６４Ｈ」（ＭＷ＝５０００～６０００、酸価＝約６０ｍｇ－ＫＯＨ／ｇ、アルカリ可溶性樹脂（Ａ－１）に該当）
　＜アルカリ可溶性樹脂－３＞　
　昭和高分子（株）製「ＳＰＣＭ－８２」（ＭＷ＝約１００００、酸価＝約２４ｍｇ－ＫＯＨ／ｇ、アクリレート系アルカリ可溶性樹脂）　 <Alkali-soluble resin-1>
“ADEP02” manufactured by Shin-Nakamura Chemical Co., Ltd. ((MW = 3500-4500, acid value = about 110 mg-KOH / g, corresponding to alkali-soluble resin (A-2))
<Alkali-soluble resin-2>
“ZCR-1664H” manufactured by Nippon Kayaku Co., Ltd. (MW = 5000 to 6000, acid value = about 60 mg-KOH / g, corresponding to alkali-soluble resin (A-1))
<Alkali-soluble resin-3>
“SPCM-82” manufactured by Showa Polymer Co., Ltd. (MW = about 10,000, acid value = about 24 mg-KOH / g, acrylate-based alkali-soluble resin)
　＜アルカリ可溶性樹脂－４＞
　５００ｍＬ４つ口フラスコにスチレン／アクリル酸樹脂、ジョンクリル６８０（ＢＡＳＦジャパン（株））６１．２ｇをプロピレングリコールモノメチルエーテルアセテート１３８．６ｇに８０℃で均一に溶解させた。これにテトラアンモニウムクロライド０．２４ｇ、ｐ－メトキシフェノール０．０９ｇを加えて溶解させ、プロピレングリコールモノメチルエーテルアセテート７１．４ｇと３，４－エポキシシクロヘキシルメチルアクリレート（サイクロマーＡ４００　ダイセル化学（株））１９．９ｇの混合液を４０分かけて滴下した。反応溶液を８０℃に保ったまま３２時間攪拌し、重量平均分子量６７００、酸価１０６ｍｇＫＯＨ／ｇの樹脂を得た。　 <Alkali-soluble resin-4>
In a 500 mL four-necked flask, 61.2 g of styrene / acrylic acid resin, Jonkrill 680 (BASF Japan Ltd.) was uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 ° C. To this, 0.24 g of tetraammonium chloride and 0.09 g of p-methoxyphenol were added and dissolved. 71.4 g of propylene glycol monomethyl ether acetate and 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A400 Daicel Chemical Co., Ltd.) 19 .9 g of the mixed solution was dropped over 40 minutes. The reaction solution was stirred for 32 hours while maintaining at 80 ° C. to obtain a resin having a weight average molecular weight of 6700 and an acid value of 106 mgKOH / g.
　＜アルカリ可溶性樹脂－５＞
　昭和高分子（株）製「ＳＰＣＭ－１２１Ｂ」（ＭＷ＝約８３００、酸価＝約８０ｍｇ－ＫＯＨ／ｇ、アクリレート系アルカリ可溶性樹脂） <Alkali-soluble resin-5>
“SPCM-121B” manufactured by Showa Polymer Co., Ltd. (MW = about 8300, acid value = about 80 mg-KOH / g, acrylate-based alkali-soluble resin)
　＜分散剤－１＞
　ビックケミー社製「ＤｉｓｐｅｒＢＹＫ－２０００」（側鎖に４級アンモニウム塩基を有するＡブロックと、４級アンモニウム塩基を有さないＢブロックからなる、アクリル系Ａ－Ｂブロック共重合体）
　＜分散剤－２＞
　ビックケミー社製「ＤｉｓｐｅｒＢＹＫ－ＬＰＮ２１１１６」（側鎖に４級アンモニウム塩基及びアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、アクリル系Ａ－Ｂブロック共重合体）
　＜分散剤－３＞
　ビックケミー社製「ＤｉｓｐｅｒＢＹＫ－１６７」（ウレタン系分散剤）
　＜分散助剤＞　
　ループリゾール社製「Ｓ１２０００」　 <Dispersant-1>
“DisperBYK-2000” (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base)
<Dispersant-2>
“DisperBYK-LPN21116” (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base and an amino group in a side chain and a B block having no quaternary ammonium base and an amino group in the side chain. )
<Dispersant-3>
“DisperBYK-167” manufactured by Big Chemie (urethane-based dispersant)
<Dispersing aid>
“S12000” manufactured by Loop Resor Co., Ltd.
　＜界面活性剤＞
　大日本インキ化学社製　メガファック　Ｆ－４７５
　＜溶剤－１＞　
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
　＜溶剤－２＞　
　ＭＢ：３－メトキシブタノール
　＜溶剤－３＞　
　ＭＢＡ：酢酸３－メトキシブチル
　＜溶剤－４＞　
　ＣＨＮ：シクロヘキサノン
　＜光重合開始剤＞　
　下記式で表される化合物。 <Surfactant>
Mega Japan F-475 manufactured by Dainippon Ink & Chemicals, Inc.
<Solvent-1>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-2>
MB: 3-methoxybutanol <Solvent-3>
MBA: 3-methoxybutyl acetate <Solvent-4>
CHN: cyclohexanone <photopolymerization initiator>
A compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　＜エチレン性不飽和化合物＞　
　ＤＰＨＡ：日本化薬（株）製　ジペンタエリスリトールヘキサアクリレート　
　＜顔料分散液－１～４の調製＞　
　表１に記載の顔料、分散剤、分散助剤、アルカリ可溶性樹脂、溶剤としてプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）とメトキシブチルアセテート（ＭＢＡ）を表１に記載の重量比で混合した。ここに、分散容器の容積の８０％のジリコニアビーズを混合した後、ピコミル分散容器に充填し、必要なリテンション時間にて分散させて各顔料分散液を調製した。　 <Ethylenically unsaturated compound>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate
<Preparation of pigment dispersions 1 to 4>
The pigment, dispersant, dispersion aid, alkali-soluble resin and propylene glycol monomethyl ether acetate (PGMEA) and methoxybutyl acetate (MBA) as a solvent described in Table 1 were mixed at a weight ratio described in Table 1. Here, 80% of the volume of the dispersion container was mixed with zirconia beads, filled in a picomill dispersion container, and dispersed for a required retention time to prepare each pigment dispersion.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
　［実施例１～３、比較例１～４］
　上記で調製された顔料分散液と、表２に示す成分とを表２に示す割合で配合、攪拌してそれぞれ着色感光性組成物塗布液を調製した。得られ着色感光性組成物溶液を用いて、後述の方法により、略円柱状スペーサパターンを形成し、形状、段差、基板との密着性及び電圧保持率（ＶＨＲ）を評価した。結果を表２に併記した。 [Examples 1 to 3, Comparative Examples 1 to 4]
The pigment dispersion prepared above and the components shown in Table 2 were blended in the proportions shown in Table 2 and stirred to prepare colored photosensitive composition coating solutions. Using the resulting colored photosensitive composition solution, a substantially cylindrical spacer pattern was formed by the method described later, and the shape, level difference, adhesion to the substrate, and voltage holding ratio (VHR) were evaluated. The results are shown in Table 2.
　［高さの異なる着色スペーサを一括形成する方法］　
　表面にＩＴＯ膜を形成したガラス基板の該ＩＴＯ膜上に、スピナーを用いて上記感光性組成物を塗布した。次いで、１１０℃にて７０ｓ、ホットプレート上で加熱乾燥して塗布膜を形成した。乾燥膜厚は３．５μｍであった。
　得られた塗布膜に対し、直径１５μｍの円形パターンの完全透過開口部及び直径３５μｍの円形パターンの中間透過開口部を有する露光マスクを用いて露光処理を施した。中間透過開口部は、Ｃｒ酸化物の薄膜で波長３６５ｎｍにおける光透過率を１２．１％、４０５ｎｍにおける光透過率を１６．５％、４３６ｎｍにおける光透過率を１９．６％としたものである。尚、上記３点の前後及び間の光透過率は連続的であり、変曲点も存在しない。露光ギャップ（マスクと塗布面間の距離）としては、２５０μｍであった。
　また、３６５ｎｍでの強度が３２ｍＷ／ｃｍ２である紫外線を用いた。露光量としては５０ｍＪ／ｃｍ２とした。また、紫外線照射は空気下で行った。次いで、２５℃の０．１％水酸化カリウム水溶液を用いて、最小現像時間の１．６倍の時間、スプレー現像を行い、更に純水でリンスした。１２０秒でも溶けないものは現像できないこととした。
　これらの操作により、不要部分を除去したパターンを得た。当該パターンの形成された基板をオーブン中、２３０℃で２０分間加熱してパターンを硬化させ、略円柱状のスペーサパターンを得た。 [Method of forming colored spacers with different heights at once]
The said photosensitive composition was apply | coated using the spinner on this ITO film | membrane of the glass substrate which formed the ITO film | membrane on the surface. Subsequently, the coating film was formed by heating and drying on a hot plate at 110 ° C. for 70 s. The dry film thickness was 3.5 μm.
The obtained coating film was subjected to exposure treatment using an exposure mask having a circular transmission pattern having a circular pattern with a diameter of 15 μm and an intermediate transmission opening having a circular pattern with a diameter of 35 μm. The intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 12.1% at a wavelength of 365 nm, a light transmittance of 405 nm at 16.5%, and a light transmittance at 436 nm of 19.6%. . The light transmittance before and after the three points is continuous, and there is no inflection point. The exposure gap (distance between the mask and the coated surface) was 250 μm.
Further, ultraviolet rays having an intensity at 365 nm of 32 mW / cm 2 were used. The exposure amount was 50 mJ / cm 2 . Moreover, ultraviolet irradiation was performed under air. Next, spray development was performed for 1.6 times the minimum development time using a 0.1% potassium hydroxide aqueous solution at 25 ° C., and further rinsed with pure water. Those that did not melt even after 120 seconds could not be developed.
By these operations, a pattern from which unnecessary portions were removed was obtained. The board | 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.
　［着色スペーサパターンの形状計測］
　上記略円柱状の着色スペーサパターンについて、着色スペーサパターンの中軸を通る縦断面をプロファイルし、着色スペーサパターンの高さと上、下底面の断面径を計測した。計測には、株式会社菱化システム製三次元非接触表面形状計測システムＭｉｃｒｏｍａｐＭＭ３５００－Ｍ１００を用いた。 [Measurement of colored spacer pattern shape]
About the said substantially cylindrical colored spacer pattern, the longitudinal cross section which passes along the central axis of a colored spacer pattern was profiled, and the cross-sectional diameter of the height of a colored spacer pattern and an upper and lower bottom face was measured. For the measurement, a three-dimensional non-contact surface shape measurement system Micromap MM3500-M100 manufactured by Ryoka System Co., Ltd. was used.
　図１（Ａ）及び図１（Ｂ）は、上記略円柱状スペーサパターンの形状を説明するための図である。図１（Ａ）において、着色スペーサパターン１はガラス基板２上に凸状に形成されており、平面視略円形状の輪郭を有している。図１（Ｂ）は、図１（Ａ）の着色スペーサパターン１の中軸３を通るＸ－Ｘ断面図である。図１（Ｂ）において、着色スペーサパターン１は略矩形状の輪郭を有している。かかる輪郭を着色スペーサパターン１のプロファイル４とし、プロファイル４のパターン側面部４１とガラス基板２との交点を交点Ａ，Ａ’とする。ガラス基板２の表面からプロファイル４の最高位置の点までの距離がパターン高さＨであり、交点Ａと交点Ａ’との距離が下断面径Ｌである。 FIGS. 1A and 1B are diagrams for explaining the shape of the substantially cylindrical spacer pattern. In FIG. 1A, the colored spacer pattern 1 is formed in a convex shape on a glass substrate 2 and has a substantially circular outline in plan view. FIG. 1B is an XX cross-sectional view through the central axis 3 of the colored spacer pattern 1 of FIG. In FIG. 1B, the colored spacer pattern 1 has a substantially rectangular outline. Such an outline is defined as a profile 4 of the colored spacer pattern 1, and intersections between the pattern side surface 41 of the profile 4 and the glass substrate 2 are defined as intersections A and A '. The distance from the surface of the glass substrate 2 to the highest point of the profile 4 is the pattern height H, and the distance between the intersection A and the intersection A ′ is the lower cross-sectional diameter L.
　［段差の評価］
　完全透過開口部の着色スペーサパターンの高さと中間透過開口部の着色スペーサパターンの高さの差異（ΔＨ）が０．３５μｍ超過０．８μｍ以下のものを○、０．２５μｍ以上０．４μｍ以下のものを△、０．２５μｍ未満のものを×とした。結果を表２に示した。　 [Evaluation of steps]
The difference (ΔH) between the height of the colored spacer pattern in the completely transmissive opening and the height of the colored spacer pattern in the intermediate transmissive opening is more than 0.35 μm and not more than 0.8 μm, and 0.25 μm to 0.4 μm The thing was made into (triangle | delta) and less than 0.25 micrometer was set to x. The results are shown in Table 2.
　［密着性の評価］　
　　上記のようにして、中間透過開口部のサイズが５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２５、３０、３５、４０、４５、５０μｍの中間透過開口部を２４個ずつ設けたマスクを使って、サイズの異なるパターンを２４個ずつ形成した。２４個のパターンが１個も消失しない、最も小さい中間透過開口部のサイズ（直径）を測定した。そのサイズが１５μｍ以下のものを○、１５μｍを超えるものを×とした。結果を表２に示した。 [Evaluation of adhesion]
As described above, the size of the intermediate transmission opening is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35. 24 patterns of different sizes were formed using a mask provided with 24 intermediate transmission openings of 40, 45, and 50 μm. The size (diameter) of the smallest intermediate transmission aperture where no 24 patterns disappeared was measured. Those having a size of 15 μm or less were rated as “◯” and those having a size exceeding 15 μm were rated as “×”. The results are shown in Table 2.
　［電圧保持率（ＶＨＲ）の評価］
　以下で説明した方法により、電圧保持率（ＶＨＲ）の評価を行い、結果を表２に示した。
　＜液晶セルの作製＞
　５ｃｍ角の片全面にＩＴＯ膜を形成した電極基板Ａ（イーエッチシー製、評価用ガラスＩＴＯベタ）と、２．５ｃｍ角の同ガラス基板の片面中央部に、２ｍｍ幅の取り出し電極がつながった１ｃｍ角のＩＴＯ膜を形成した電極基板Ｂ（イーエッチシー製、評価用ガラスＳＺ－Ｂ１１１ＭＩＮ（Ｂ））を用意した。　 [Evaluation of voltage holding ratio (VHR)]
The voltage holding ratio (VHR) was evaluated by the method described below, and the results are shown in Table 2.
<Production of liquid crystal cell>
An extraction substrate having a width of 2 mm was connected to the center of one side of the 2.5 cm square glass substrate and the electrode substrate A (ETHCY, glass ITO solid for evaluation) having an ITO film formed on the entire surface of a 5 cm square piece. An electrode substrate B (manufactured by ECH, evaluation glass SZ-B111MIN (B)) on which a 1 cm square ITO film was formed was prepared.
　電極基板Ａの上に、各着色感光性組成物溶液を塗布し、１分間真空乾燥後、ホットプレート上で１１０℃にて７０ｓプリベークし、乾燥膜厚３．５μｍの塗布膜を得た。その後、外縁部が２ｍｍマスキングして、それぞれ３ｋＷ高圧水銀を用い５０ｍＪ／ｃｍ２の露光条件にて画像露光を施した。次いで、２５℃の約０．１重量％の水酸化カリウム水溶液を用い、２５℃において水圧０．１５ＭＰａのシャワー現像を施した後、純水にて現像を停止し、水洗スプレーにてリンスした。シャワー現像時間は、１０～１２０秒間の間で調整し、感光層が溶解除去される時間（ブレークタイム）の約１．６倍とした。１２０秒でも溶けないものは現像できないこととした。 Each colored photosensitive composition solution was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then pre-baked at 110 ° C. for 70 s on a hot plate to obtain a coating film having a dry film thickness of 3.5 μm. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed using 3 kW high-pressure mercury under exposure conditions of 50 mJ / cm 2 . Next, shower development with a water pressure of 0.15 MPa was performed at 25 ° C. using an approximately 0.1 wt% potassium hydroxide aqueous solution at 25 ° C., and then development was stopped with pure water and rinsed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was about 1.6 times the time (break time) for dissolving and removing the photosensitive layer. Those that did not melt even after 120 seconds could not be developed.
　こうして画像形成された電極基板を２３０℃で２０分間ポストベークし、レジストが施された電極基板を得た（レジスト基板）。その後、レジスト基板にポリイミド溶液を塗布し、ホットプレート上で７０℃にて２分間プリベークし、２２０℃で２４分間ポストベークした。こうして得られたレジスト基板を２．５ｃｍ角の基板にカットし、評価用電極基板Ａを完成した。 The electrode substrate thus image-formed was post-baked at 230 ° C. for 20 minutes to obtain a resist-coated electrode substrate (resist substrate). Thereafter, a polyimide solution was applied to the resist substrate, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes. The resist substrate thus obtained was cut into a 2.5 cm square substrate to complete an evaluation electrode substrate A.
　一方、電極基板Ｂの上にも、ポリイミド溶液を塗布し、ホットプレート上で７０℃にて２分間プリベークし、２２０℃で２４分間ポストベークし、評価用電極基板Ｂを完成した。
　その後、電極基板Ｂの外周上に、ディスペンサーを用いて、直径５μｍのシリカビーズを含有するエポキシ樹脂系シール剤を塗布した後、電極基板Ｂの表側（シール剤側）に評価用電極基板Ａの塗布面を圧着したまま貼り付けて、空セルが完成した。熱風循環炉内で１８０℃で２時間加熱した。　 On the other hand, a polyimide solution was applied also onto the electrode substrate B, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes to complete an evaluation electrode substrate B.
Thereafter, an epoxy resin sealant containing silica beads having a diameter of 5 μm is applied on the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A for evaluation is placed on the front side (the sealant side) of the electrode substrate B. The application surface was pasted and bonded to complete the empty cell. Heating was performed at 180 ° C. for 2 hours in a hot air circulating furnace.
　こうして得られた空セルに、液晶（メルクジャパン社製ＭＬＣ－６６０８）を注入し、周辺部をＵＶ硬化型シール剤によって封止し、電圧保持率測定用液晶セルを完成した。 A liquid crystal (MLC-6608 manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained, and the peripheral portion was sealed with a UV curable sealant to complete a voltage holding ratio liquid crystal cell.
　＜電圧保持率（ＶＨＲ）の評価＞
　上記液晶セルを、アニール処理（熱風循環炉内で１０５℃、２．５時間加熱）した後、評価用電極基板Ａ、Ｂに電圧５Ｖで、０．６Ｈｚ、フレーム時間１６６７ｍｓｅｃの条件で印加し、電圧保持率を（株）東陽テクニカ製「ＶＨＲ－６２５４型」にて測定した。　 <Evaluation of voltage holding ratio (VHR)>
After the above liquid crystal cell is annealed (heated at 105 ° C. for 2.5 hours in a hot air circulating furnace), it is applied to the electrode substrates A and B for evaluation at a voltage of 5 V, 0.6 Hz, and a frame time of 1667 msec. The voltage holding ratio was measured by “VHR-6254 type” manufactured by Toyo Corporation.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　表２の結果から、本発明の着色感光性組成物によれば、完全透過開口部と中間透過開口部パターンの形状の形成、段差のコントロール、密着性の良い、かつ液晶の電圧保持率に優れる着色スペーサを得ることが可能であり、高さの異なる着色スペーサを一括形成する方法に有用であることが分かる。 From the results of Table 2, according to the colored photosensitive composition of the present invention, the formation of the shape of the completely transmissive opening portion and the intermediate transmissive opening portion pattern, the control of the level difference, the good adhesion, and the liquid crystal voltage holding ratio are excellent. It can be seen that it is possible to obtain colored spacers, which is useful for a method of forming colored spacers having different heights at once.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１１年１０月２５日出願の日本特許出願（特願２０１１－２３３９００）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on October 25, 2011 (Japanese Patent Application No. 2011-233900), the contents of which are incorporated herein by reference.
　本発明の着色感光性組成物は、液晶ディスプレイ等のカラーフィルターにおいて、着色スペーサ等を形成する際に好適に用いられる着色感光性組成物であって、特にフォトリソグラフィー法により高さの異なる着色スペーサを一括形成する場合に、形状の形成、段差、密着性及び液晶の電気信頼性に優れる。本発明は、高品質なカラーフィルターや液晶表示装置等を提供することができる。 The colored photosensitive composition of the present invention is a colored photosensitive composition that is suitably used when forming a colored spacer or the like in a color filter such as a liquid crystal display, and is a colored spacer having a different height by a photolithography method in particular. In the case of forming all together, it is excellent in shape formation, level difference, adhesion, and liquid crystal electrical reliability. The present invention can provide a high-quality color filter, a liquid crystal display device, and the like.

Claims (14)

  1. 　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）エチレン性不飽和化合物、（ｅ）溶剤、及び（ｆ）分散剤を含有する、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成するために用いられる着色感光性組成物であって、
    　（ｂ）アルカリ可溶性樹脂として、下記アルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）のうち少なくとも一方を含み、
    　（ｆ）分散剤として、窒素原子を含有するアクリル系ブロック共重合体を含み、
    　（ｄ）エチレン性不飽和化合物に対する（ｂ）アルカリ可溶性樹脂の重量比が、７未満であり、
    　着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合が１２重量％以上である着色感光性組成物。　
    ＜アルカリ可溶性樹脂（Ａ－１）＞
    　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸無水物を反応させることにより得られる樹脂
    ＜アルカリ可溶性樹脂（Ａ－２）＞
    　エポキシ樹脂に、α，β－不飽和モノカルボン酸又はエステル部分にカルボキシル基を有するα，β－不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール及び多塩基酸無水物を反応させることにより得られる樹脂     (A) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, A colored photosensitive composition used to collectively form colored spacers having different thicknesses,
    (B) the alkali-soluble resin includes at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2);
    (F) As a dispersant, an acrylic block copolymer containing a nitrogen atom is included,
    (D) the weight ratio of (b) alkali-soluble resin to ethylenically unsaturated compound is less than 7,
    A colored photosensitive composition in which the total proportion of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition is 12% by weight or more.
    <Alkali-soluble resin (A-1)>
    Resin obtained by adding α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to epoxy resin, and further reacting with a polybasic acid anhydride <Alkali-soluble resin (A-2)>
    Adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, and further reacting a polyhydric alcohol and a polybasic acid anhydride. Resin obtained by
  2. 　着色感光性組成物中の全固形分に対するアルカリ可溶性樹脂（Ａ－１）及びアルカリ可溶性樹脂（Ａ－２）の合計の割合が２０重量％以上である請求項１に記載の着色感光性組成物。 2. The colored photosensitive composition according to claim 1, wherein the total proportion of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition is 20% by weight or more. .
  3. 　（ａ）着色剤の含有比率が、着色感光性組成物中の全固形分に対し３０重量％未満である請求項１又は２に記載の着色感光性組成物。 (A) The colored photosensitive composition according to claim 1 or 2, wherein the content ratio of the coloring agent is less than 30% by weight with respect to the total solid content in the colored photosensitive composition.
  4. 　（ａ）着色剤の含有比率が、着色感光性組成物中の全固形分に対し２５重量％以上である請求項１乃至３のいずれか１項に記載の着色感光性組成物。 The colored photosensitive composition according to any one of claims 1 to 3, wherein the content ratio of (a) the colorant is 25% by weight or more based on the total solid content in the colored photosensitive composition.
  5. 　（ａ）着色剤として、以下の（１）赤色顔料を含み、かつ以下の（２）青色顔料及び以下の（３）紫色顔料のうち少なくとも一方を含む請求項１乃至４のいずれか１項に記載の着色感光性組成物。
    　　（１）Ｃ．Ｉ．ピックメントレッド１７７、２５４から選ばれる赤色顔料
    　　（２）Ｃ．Ｉ．ピックメントブルー１５：６である青色顔料
    　　（３）Ｃ．Ｉ．ピックメントバイオレッド２３である紫色顔料     (A) The coloring agent according to any one of claims 1 to 4, comprising (1) a red pigment as described below and at least one of the following (2) blue pigment and the following (3) purple pigment: The colored photosensitive composition as described.
    (1) C.I. I. Red pigments selected from among pigment reds 177 and 254 (2) C.I. I. Blue pigment which is a pigment blue 15: 6 (3) C.I. I. Purple pigment which is Pickment Bio Red 23
  6. 　（ａ）着色剤として、Ｃ．Ｉ．ピックメントレッド２５４及びＣ．Ｉ．ピックメントブルー１５：６を含む請求項１乃至４のいずれか１項に記載の着色感光性組成物。 (A) As a colorant, C.I. I. Pickment Red 254 and C.I. I. The colored photosensitive composition according to any one of claims 1 to 4, comprising a pigment blue 15: 6.
  7. 　（ｆ）分散剤として、側鎖に４級アンモニウム塩基及びアミノ基のうち少なくとも一方を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む請求項１乃至６のいずれか１項に記載の着色感光性組成物。 (F) AB block copolymer comprising, as a dispersant, an A block having at least one of a quaternary ammonium base and an amino group in a side chain, and a B block having no quaternary ammonium base and an amino group. And a colored photosensitive composition according to any one of claims 1 to 6, comprising at least one of a BB block copolymer and a BAB block copolymer.
  8. 　（ｆ）分散剤として、側鎖に４級アンモニウム塩基及びアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む請求項１乃至６のいずれか１項に記載の着色感光性組成物。 (F) AB block copolymer and B-A comprising A block having a quaternary ammonium base and an amino group in the side chain, and a B block having no quaternary ammonium base and amino group as a dispersant. The colored photosensitive composition according to any one of claims 1 to 6, comprising at least one of -B block copolymers.
  9. 　（ｆ）分散剤として、側鎖に４級アンモニウム塩基を有さずアミノ基を有するＡブロックと、４級アンモニウム塩基及びアミノ基を有さないＢブロックからなる、Ａ－Ｂブロック共重合体及びＢ－Ａ－Ｂブロック共重合体のうち少なくとも一方を含む請求項１乃至６のいずれか１項に記載の着色感光性組成物。 (F) an AB block copolymer comprising, as a dispersant, an A block having an amino group without a quaternary ammonium base in the side chain, and a B block having a quaternary ammonium base and no amino group; The colored photosensitive composition according to any one of claims 1 to 6, comprising at least one of a BAB block copolymer.
  10. 　（ｃ）光重合開始剤として、オキシムエステル化合物を含む請求項１乃至９のいずれか１項に記載の着色感光性組成物。 (C) The colored photosensitive composition according to any one of claims 1 to 9, comprising an oxime ester compound as a photopolymerization initiator.
  11. 　請求項１乃至１０のいずれか１項に記載の着色感光性組成物により一括形成された高さの異なる着色スペーサ。 Colored spacers having different heights, which are collectively formed from the colored photosensitive composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の着色スペーサを備えるカラーフィルター。 A color filter comprising the colored spacer according to claim 11.
  13. 　請求項１２に記載のカラーフィルターを備える液晶表示装置。 A liquid crystal display device comprising the color filter according to claim 12.
  14. 　請求項１乃至１０のいずれか１項に記載の着色感光性組成物を用いて、フォトリソグラフィー法により高さの異なる着色スペーサを一括形成する方法。 A method of collectively forming colored spacers having different heights by a photolithography method using the colored photosensitive composition according to any one of claims 1 to 10.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017053942A (en) * 2015-09-08 2017-03-16 三菱化学株式会社 Photosensitive coloring composition, cured product, colored spacer, and image display device
KR20170045125A (en) 2015-10-16 2017-04-26 신닛테츠 수미킨 가가쿠 가부시키가이샤 Photosensitive resin composition for light-shielding film with the role of spacer, light-shielding film thereof, lcd with that film, and manufacturing process for them
WO2017110893A1 (en) * 2015-12-24 2017-06-29 三菱化学株式会社 Photosensitive coloring composition, cured product, colored spacer, and image display device
KR20180098169A (en) 2017-02-24 2018-09-03 신닛테츠 수미킨 가가쿠 가부시키가이샤 Photosensitive resin composition for light-sielding film with the role of spacer, light-sielding film thereof, lcd with that film, and manufacturing process for them
KR20180111661A (en) 2017-03-31 2018-10-11 신닛테츠 수미킨 가가쿠 가부시키가이샤 Photosensitive resin composition, light-shielding film thereof, and manufacturing process of lcd with that film
JP2019133167A (en) * 2013-09-25 2019-08-08 三菱ケミカル株式会社 Photosensitive coloring composition, coloring spacer, and image display device
CN113608408A (en) * 2015-03-11 2021-11-05 三菱化学株式会社 Photosensitive coloring composition for forming colored spacer, cured product, colored spacer, and image display device

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5962865B1 (en) * 2014-08-20 2016-08-03 東レ株式会社 Photosensitive coloring composition and method for producing solid-state imaging device using the same
KR102218948B1 (en) 2014-09-23 2021-02-23 동우 화인켐 주식회사 Black photosensitive resin composition, and black matrix and column spacer for liquid crystal display manufactured thereby
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TWI789434B (en) * 2017-09-26 2023-01-11 日商大阪有機化學工業股份有限公司 Photosensitive resin composition for forming photo-spacer, method for forming photo-spacer, substrate with photo-spacer, and color filter
KR102386493B1 (en) * 2018-01-15 2022-04-14 동우 화인켐 주식회사 Colored photosensitive resin composition, color filter and image display device using the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008015393A (en) * 2006-07-10 2008-01-24 Jsr Corp Radiation-sensitive composition for colored layer formation, color filter and color liquid crystal display element
JP2008143941A (en) * 2006-12-06 2008-06-26 Showa Highpolymer Co Ltd Photosensitive resin and photosensitive resin composition containing the same
JP2009014927A (en) * 2007-07-03 2009-01-22 Mitsubishi Chemicals Corp Colored photopolymerizable composition, color filter and liquid crystal display device
JP2009031778A (en) * 2007-06-27 2009-02-12 Mitsubishi Chemicals Corp Photosensitive composition, method, cured product, and liquid crystal display device
JP2009053652A (en) * 2007-07-27 2009-03-12 Mitsubishi Chemicals Corp Coloring composition for color filter, color filter and liquid crystal display
JP2009069822A (en) * 2007-08-22 2009-04-02 Mitsubishi Chemicals Corp Resin black matrix, light blocking photosensitive resin composition, tft element substrate and liquid crystal display device

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08234212A (en) 1995-02-28 1996-09-13 Casio Comput Co Ltd Liquid crystal display element
JPH11337949A (en) * 1998-05-28 1999-12-10 Hitachi Chem Co Ltd Photosensitive film for forming colored resin spacer
JP4561062B2 (en) * 2003-08-07 2010-10-13 三菱化学株式会社 Photosensitive colored resin composition for color filter, color filter, and liquid crystal display device
JP4794870B2 (en) * 2005-02-24 2011-10-19 東京応化工業株式会社 Photosensitive resin composition for forming light shielding layer, light shielding layer and color filter
CN101379132B (en) * 2006-03-10 2011-07-27 三菱化学株式会社 Curable composition, color filter, and liquid crystal display device
JP2009003442A (en) * 2007-05-23 2009-01-08 Mitsubishi Chemicals Corp Photosensitive resin composition, liquid crystal alignment control rib, spacer, color filter and image display device
WO2008153000A1 (en) * 2007-06-11 2008-12-18 Mitsubishi Chemical Corporation Photosensitive color resin composition for color filter, color filter, liquid crystal display, and organic el display
KR20140042931A (en) * 2007-06-21 2014-04-07 미쓰비시 가가꾸 가부시키가이샤 Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display and organic el display
JP5487564B2 (en) * 2007-06-21 2014-05-07 三菱化学株式会社 Colored resin composition, color filter, liquid crystal display device and organic EL display
DE102007033191A1 (en) * 2007-07-17 2009-01-22 Clariant International Ltd. Finely divided epsilon-copper phthalocyanine pigment preparation
JP5407199B2 (en) * 2008-07-03 2014-02-05 三菱化学株式会社 Pigment dispersion, coloring composition, color filter, liquid crystal display device and organic EL display
JP5018691B2 (en) * 2008-08-13 2012-09-05 三菱化学株式会社 Pigment dispersion, coloring composition for color filter, color filter, liquid crystal display device, and organic EL display
KR101148548B1 (en) * 2008-09-30 2012-05-21 코오롱인더스트리 주식회사 Photopolymerizable resin composition
WO2010038978A2 (en) * 2008-09-30 2010-04-08 Kolon Industries, Inc. Photopolymer resin composition
JP5363844B2 (en) * 2009-03-17 2013-12-11 株式会社Ｄｎｐファインケミカル Alkali-soluble photosensitive coloring composition and color filter
JP5120349B2 (en) * 2009-08-03 2013-01-16 三菱化学株式会社 Photosensitive colored resin composition for color filter, color filter, and liquid crystal display device
JP5760374B2 (en) * 2009-10-23 2015-08-12 三菱化学株式会社 Ketoxime ester compounds and uses thereof
JP2011107707A (en) * 2009-11-18 2011-06-02 Kolon Industries Inc Photosensitive resin composition
JP2011107474A (en) * 2009-11-18 2011-06-02 Toppan Printing Co Ltd Color filter substrate and liquid crystal display device
JP5429721B2 (en) * 2012-06-25 2014-02-26 和雄 齋藤 Manual noodle punch

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008015393A (en) * 2006-07-10 2008-01-24 Jsr Corp Radiation-sensitive composition for colored layer formation, color filter and color liquid crystal display element
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