WO2015046178A1 - Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion - Google Patents
Photosensitive coloring composition, black matrix, coloring spacer, image display device, and pigment dispersion Download PDFInfo
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- WO2015046178A1 WO2015046178A1 PCT/JP2014/075144 JP2014075144W WO2015046178A1 WO 2015046178 A1 WO2015046178 A1 WO 2015046178A1 JP 2014075144 W JP2014075144 W JP 2014075144W WO 2015046178 A1 WO2015046178 A1 WO 2015046178A1
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- 0 *C([C@@]1C2=C(c(c(*)c(*)c(*)c3*)c3N3)C3=O)C(OC(C3=C(c(c(*)c(*)c(*)c4*)c4N4)C4=O)=O)=C3C(*)=C1OC2=O Chemical compound *C([C@@]1C2=C(c(c(*)c(*)c(*)c3*)c3N3)C3=O)C(OC(C3=C(c(c(*)c(*)c(*)c4*)c4N4)C4=O)=O)=C3C(*)=C1OC2=O 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N c(cc1)ccc1-c1ccccc1 Chemical compound c(cc1)ccc1-c1ccccc1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BUJFTKPQXSIZFX-UHFFFAOYSA-N CCC(C)(C)NC Chemical compound CCC(C)(C)NC BUJFTKPQXSIZFX-UHFFFAOYSA-N 0.000 description 1
- TVNRPMNPOQGGND-UHFFFAOYSA-N CCN(C1C2C(C3=C4)=CC(C(CCC5CCCC5)NOC(C)O)=CC12)C3=CCC4C(C1=C(C)CCC=C1)=O Chemical compound CCN(C1C2C(C3=C4)=CC(C(CCC5CCCC5)NOC(C)O)=CC12)C3=CCC4C(C1=C(C)CCC=C1)=O TVNRPMNPOQGGND-UHFFFAOYSA-N 0.000 description 1
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- 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
- G02F1/133512—Light shielding layers, e.g. black matrix
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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
- G03F7/0005—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
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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
- 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
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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
- 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
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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
- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
Definitions
- the present invention relates to a photosensitive coloring composition, a black matrix, a coloring spacer, and an image display device.
- a photosensitive coloring composition excellent in shielding property and plate-making characteristic, and its use.
- the black matrix for a liquid crystal display element is used to prevent light leakage from the drive electrodes in the liquid crystal display element.
- a black matrix is a pattern of a light-shielding material in the form of stripes or lattices formed by using a photolithography method on a transparent substrate such as glass or plastic sheet that is paired with a TFT (Thin Film Transistor) element substrate. is there.
- a color filter on array method COA method
- a black matrix on array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed.
- the black matrix has a volume resistivity above a certain level and a relative dielectric constant below a certain level so as not to cause a short circuit of an electric circuit even if it is directly mounted on a TFT element. Is required.
- a black matrix using a plurality of types of organic coloring pigments and carbon black as a pigment has been proposed (for example, see Patent Document 1).
- photosensitive compositions for black matrix using organic black pigments as pigments are also known.
- aniline black for example, see Patent Document 2
- perylene black for example, see Patent Document 3
- organic pigments for example, Patent Document 4
- This document describes that the pigment is used for forming a red layer, a blue layer and a green layer of a color filter.
- this pigment is used also as an organic black pigment for electrophoretic displays (for example, refer patent document 5).
- Japanese Unexamined Patent Publication No. 2009-75446 Japanese Laid-Open Patent Publication No. 8-44049 Japanese Unexamined Patent Publication No. 2006-235153 Japanese National Table 2002-528448 Japan Special Table 2012-515240
- the photosensitive composition described in Patent Document 1 has a low shielding ratio (optical density) of the organic coloring pigment, and the film thickness is increased in order to obtain a sufficient optical density. I found it necessary to do.
- the aniline black and perylene black described in Patent Documents 2 and 3 have poor dispersibility, and it is necessary to use a large amount of a dispersant to disperse, which may cause problems in plate-making properties. I found out. In addition, it was found that the shielding rate (optical density) was not sufficient.
- Patent Documents 4 and 5 have no description or suggestion about using a bis-oxodihydro-indoleylene-benzofuran colorant as a shielding agent used in an image display device, and when used as a shielding agent used in an image display device.
- the characteristics such as the optical density, dispersibility and plate-making property are also unknown.
- the present invention has been made in view of the above-described conventional circumstances, and provides a photosensitive coloring composition having excellent light-shielding properties, excellent dispersibility and plate making properties, and exhibiting a sufficiently low relative dielectric constant. With the goal.
- the organic coloring pigment having a specific structure is used as the coloring material in the photosensitive coloring composition, and a specific dispersant is used.
- the present invention has the following configurations [1] to [17].
- a photosensitive coloring composition containing at least (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein (A) the coloring material is (A-1) an organic black pigment that is a compound represented by the following general formula (1), a geometric isomer, a salt thereof, or a salt of the geometric isomer, and the dispersant (B) is 4
- a photosensitive coloring composition comprising a polymer dispersant having a quaternary ammonium base as a functional group.
- R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9, and R 10 are independently of each other hydrogen atoms, halogen atoms, R 11 , COOH, COOR 11 , COO ⁇ , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11.
- R 10 may be directly bonded to each other, or may be bonded to each other by an oxygen atom, sulfur atom, NH or NR 11 bridge; R 11 and R 12 are independently of each other; An alkyl group having 1 to 12 carbon atoms,
- R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom
- R 3 and R 8 are each independently a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 —
- R 1 is the same as R 6
- R 2 is the same as R 7
- R 3 is the same as R 8
- the photosensitive coloring composition according to [1] wherein R 4 is the same as R 9 and R 5 is the same as R 10 .
- the content ratio of the (A-1) organic black pigment is 30 to 90 mass% and the content ratio of the (A-2) organic color pigment is 10 to 70 mass% with respect to 100 mass% of the color material (A).
- the photosensitive coloring composition according to any one of [1] to [7], wherein the (A) coloring material further contains (A-3) carbon black.
- the content ratio of the (A-1) organic black pigment is 50 to 90 mass% and the content ratio of (A-3) carbon black is 10 to 50 mass% with respect to 100 mass% of the color material (A).
- the photosensitive coloring composition as described in [8].
- An image display device comprising the black matrix according to [12] or the colored spacer according to [13].
- R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom
- R 3 and R 8 are independently a hydrogen atom, NO 2, OCH 3, OC 2 H 5, a bromine atom, a chlorine atom, CH 3, C 2 H 5 , N (CH 3) 2, N (CH 3) (C 2 H 5), N (C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 —
- R 1 is the same as R 6
- R 2 is the same as R 7
- R 3 is the same as R 8
- R 4 is the same as R 9 and R 5 is the same as R 10 .
- the photosensitive coloring composition of the present invention includes an organic black pigment having a specific structure, so that the amount of the dispersing agent can be reduced at the time of preparing the pigment dispersion, thereby exhibiting excellent plate making characteristics and dispersibility. Also excellent. Therefore, the black matrix formed from the photosensitive coloring composition of the present invention exhibits excellent light shielding properties. Further, the black matrix and the colored spacer of the present invention exhibit a sufficiently low relative dielectric constant so as not to cause a short circuit or malfunction even when formed on the TFT element substrate.
- the image display device having the black matrix of the present invention is free from problems such as TFT failure and liquid crystal drive disturbance, and is excellent in reliability.
- FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element.
- (meth) acryl means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
- (co) polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer).
- acid (anhydride) means to include both acids and anhydrides.
- acrylic resin means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic ester having a carboxyl group.
- the term “monomer” is a term corresponding to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a monomer (monomer) in a narrow sense. It is.
- the “total solid content” means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
- the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
- the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
- the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
- photosensitive coloring composition The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “photosensitive coloring composition” or “colored resin composition”)
- Photopolymerization initiator is contained as an essential component, and if necessary, adhesion improvers such as organic solvents and silane coupling agents, coating It contains other compounding components such as property improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc., and each compounding component is usually dissolved or dispersed in an organic solvent. used.
- the coloring material (A) used in the present invention includes (A-1) a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or an organic black pigment that is a salt of the geometric isomer. .
- R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- the compound represented by general formula (1) When the compound represented by general formula (1) is anionic, its charge can be any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal.
- the geometric isomer of the compound represented by the general formula (1) is anionic, it is preferably a similar salt.
- R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are independently of each other preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
- R 3 and R 8 are preferably independently of each other a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 — , more preferably a hydrogen atom or SO 3 H.
- R 1 and R 6 are preferably each independently a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
- at least one combination selected from the group consisting of R 1 and R 6 , R 2 and R 7 , R 3 and R 8 , R 4 and R 9 , and R 5 and R 10 is the same, and more preferably R 1 is the same as R 6 , R 2 is the same as R 7 , R 3 is the same as R 8 , R 4 is the same as R 9 , and R 5 is the same as R 10 Are the same.
- alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl Group, nonyl group, decyl group, undecyl group or dodecyl group.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, tuzyl group, norbornyl group, bornyl group, norcaryl group. , Caryl group, menthyl group, norpinyl group, pinyl group, 1-adamantyl group or 2-adamantyl group.
- alkenyl group having 2 to 12 carbon atoms examples include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene.
- Examples of the cycloalkenyl group having 3 to 12 carbon atoms include a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen-1-yl group, , 4-Cyclohexadien-1-yl group, 1-p-menten-8-yl group, 4 (10) -tgen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -Yl group, 7,7-dimethyl-2,4-norcaradien-3-yl group or camphenyl group.
- alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl.
- the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- a preferable organic black pigment (A-1) is a compound represented by the following general formula (2).
- organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
- the organic black pigment (A-1) is preferably used after being dispersed by a dispersant, a solvent and a method described later.
- dispersibility and storage stability may be improved.
- the photosensitive coloring composition of the present invention may contain a color material other than (A-1) as the color material (A).
- a color material other than (A-1) as the color material (A).
- dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
- (A-2) organic color pigments and / or (A-3) carbon black are preferably used.
- an organic coloring pigment is a powder containing an organic compound used for coloring as a component, and means a thing unnecessary for water or oil.
- A-2) Various colors such as blue pigments, green pigments, red pigments, yellow pigments, purple pigments, orange pigments, brown pigments, black pigments other than (A-1) and (A-3) as organic coloring pigments
- Organic pigments can be used.
- organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, and indanthrene
- various inorganic pigments can be used.
- the color of the pigment means a color exhibited when a photosensitive coloring composition is formed by using the pigment alone as a coloring material, unless otherwise specified. That is, for example, a black pigment means a pigment that exhibits a black color when a photosensitive coloring composition is formed using the pigment alone as a colorant.
- pigments that can be used in the present invention are shown by pigment numbers below.
- terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
- red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172
- C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.
- C.I. I. Pigment Red 177, 254, and 272 are preferably used.
- a red pigment having a low ultraviolet absorptivity Is C.I. I. It is more preferable to use CI Pigment Red 254,272.
- 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. In terms of dispersibility and light shielding properties, C.I. I. Pigment Blue 15: 6, 16, and 60 are preferably used. When the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From the viewpoint, C.I. I. More preferably, CI Pigment Blue 60 is used.
- green pigments examples 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.
- yellow pigments examples include C.I. I.
- 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.
- Orange (orange) pigments include 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. In terms of dispersibility and light shielding properties, C.I. I. Pigment Orange 43, 64, and 72 are preferably used. When the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. Is C.I. I. More preferably, CI pigment oranges 64 and 72 are used.
- C.I. I. Pigment Violet 1 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.
- C.I. I. Pigment Violet 23 and 29 are preferably used, and when the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate. . I. More preferably, pigment violet 29 is used.
- Color index pigment blue 60 or 15 6 Red: Color index pigment red 177, 254, or 272
- Purple Color index pigment violet 23 or 29
- Orange Color index pigment orange 43, 64 or 72
- the color combination is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment, an orange pigment and a purple pigment Etc.
- a dye may be used in place of (A-2) the organic color pigment, and a dye may be used in addition to (A-2) the organic color pigment.
- the dye that can be used as the color material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
- the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I.
- Direct Yellow 12 C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
- anthraquinone dyes examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
- Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.
- a black pigment other than (A-1) can also be used in the photosensitive coloring composition of the present invention.
- Black pigments other than (A-1) may be used singly or as a mixture of red, green, blue and the like.
- These color materials can be appropriately selected from inorganic or organic pigments and dyes.
- Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No.
- C.I. I Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.
- black color material examples include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black.
- (A-3) carbon black is preferably used as a color material other than the (A-1) organic black pigment from the viewpoints of light shielding rate and image characteristics.
- Examples of carbon black include the following carbon black.
- the total content of Na and Ca is preferably 100 ppm or less.
- Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe.
- the ash content of etc. is contained on the order of percent.
- Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. This is because there is a case.
- the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 ml / 100 g or less. If the particle diameter is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the coating film may not have sufficient density, and if the film thickness is about 1 to 2 ⁇ m, the light is blocked. It is because there is a possibility that it may become scarce.
- DBP dibutyl phthalate
- the method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, After mixing and stirring the resin solution obtained by mixing the resin and a solvent such as cyclohexanone, toluene, xylene, and the like, and the suspension obtained by mixing carbon black and water, the carbon black and water are separated, 1. A method in which water is removed and the composition obtained by heating and kneading is formed into a sheet, pulverized and then dried; A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and the resin, separating the obtained granular material, and heating to remove the remaining solvent and water; 3.
- a solvent such as cyclohexanone, toluene, xylene, and the like
- Dissolve carboxylic acid such as maleic acid and fumaric acid in the above-mentioned solvent add carbon black, mix and dry, remove the solvent to obtain carboxylic acid-impregnated carbon black, and then add resin to it.
- a method of adding black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.
- the type of resin to be coated is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure have a stronger function as amphoteric surfactants. From the viewpoint of dispersibility and dispersion stability, it is preferable.
- Specific synthetic resins include phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin and other thermosetting resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene.
- Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used.
- the coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and when the amount is less than 1% by mass, only dispersibility and dispersion stability similar to those of the untreated carbon black can be obtained. There is a risk of not being able to. On the other hand, when it exceeds 30% by mass, the adhesiveness between the resins is strong, and it becomes a dumpling-like mass, and the dispersion may not proceed.
- the carbon black thus coated with the resin can be used as a black matrix shading material according to a conventional method, and a color filter having this black matrix as a constituent element can be prepared by a conventional method.
- a black matrix having a high light shielding rate, a low surface reflectance, and a small film thickness can be achieved at a low cost. It is presumed that the dispersibility and dispersion stability of carbon black were significantly improved with respect to the resin and solvent constituting the black matrix liquid. It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.
- pigments particularly preferably used in terms of light shielding properties include C.I. I. Pigment blue 60, C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment blue 254, C.I.
- an organic coloring pigment when included, it preferably contains at least one of the above pigments, and more preferably contains two or more.
- (A-3) carbon black resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
- These pigments are preferably used dispersed in such a manner that the average particle size is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less.
- the standard of the average particle diameter is the number of pigment particles.
- the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS).
- DLS dynamic light scattering
- a fully diluted colored resin composition usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, its concentration And measure at 25 ° C.
- (A) it is important to finely disperse the coloring material and stabilize the dispersion state, so that it is important to ensure the stability of the quality.
- (A-1) from the viewpoint of dispersibility of the organic black pigment, a polymer dispersant having a quaternary ammonium base as a functional group is included.
- the polymer dispersant further includes a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; a nitrogen-containing heterogeneous group such as pyridine, pyrimidine, and pyrazine. It may further have a functional group such as a ring-derived group.
- a polymer dispersant further having a basic functional group such as a primary, secondary or tertiary amino group; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, etc.
- (A-1) from the viewpoint of dispersibility of the organic black pigment
- (A-2) from the viewpoint of dispersibility of the organic color pigment and / or (A-3) carbon black, a quaternary ammonium base.
- a polymer dispersant having a tertiary amino group as a functional group is preferred.
- polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
- examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
- a dispersant examples include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
- the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group, and an acrylic polymer dispersant. It is particularly preferable that From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.
- urethane and acrylic polymer dispersants examples include DISPERBYK 160 to 166, 182 series (both are urethane), DISPERBYK2000, 2001, LPN21116, etc. (both are acrylic) (all manufactured by Big Chemie).
- Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000.
- examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
- polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
- Aromatic diisocyanates hexamethylene diisocyanates, lysine methyl ester diisocyanates, 2,4,4-trimethylhexamethylene diisocyanates, dimer acid diisocyanates and other aliphatic diisocyanates, isophorone diisocyanates, 4,4'-methylenebis (cyclohexyl isocyanate), ⁇ , ⁇ Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetra Aliphatic diisocyanates having an aromatic ring such as tilxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate Examples thereof include triiso
- polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
- the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
- an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like.
- Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
- Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
- polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. A mixture of two or more of the above.
- Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
- alkylene oxides such as poly (poly And oxytetramethylene) adipate.
- the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
- Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, , 6-hexanediol, 2-methyl-2,4 Pentanediol, 2,2,
- Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned. These may be used alone or in combination of two or more.
- the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
- Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
- the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
- Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl
- examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero 6-membered rings such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned.
- nitrogen-containing heterocycles preferred are an imidazole ring or a triazole ring.
- these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
- specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.
- N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable. These may be used alone or in combination of two or more.
- the preferred blending ratio of the raw materials for producing the urethane polymer dispersant is 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound.
- the production of the urethane-based polymer dispersant is performed according to a known method for producing a polyurethane resin.
- a solvent for production usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of
- a urethanization reaction catalyst is usually used.
- the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned. These may be used alone or in combination of two or more.
- the introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
- the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.
- the weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.
- an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.
- Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid.
- Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used alone or in combination of two or more.
- Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives
- the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group.
- the block may contain a partial structure derived from the unsaturated group-containing monomer not containing the functional group. May be contained in the A block in any form of random copolymerization or block copolymerization.
- content in the A block of the partial structure which does not contain a functional group is 80 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less.
- the B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. These may be contained in the B block in any form of random copolymerization or block copolymerization.
- the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
- the living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- M is a metal atom
- s and t are each an integer of 1 or more.
- the polymerization active species is a radical, and is represented by the following scheme, for example.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- j and k are each an integer of 1 or more
- R a is a hydrogen atom or 1
- R b is a hydrogen atom different from R a or a monovalent organic group.
- the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer.
- / B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio). Outside this range, good heat resistance and dispersibility cannot be achieved. There is.
- the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. Outside the range, it may not be possible to combine good heat resistance and dispersibility.
- Such a block copolymer usually contains an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, Preferably it is 10 mgKOH / g or more, More preferably, it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more, Preferably it is 90 mgKOH / g or less, More preferably, it is 80 mgKOH / g or less, More preferably, it is 75 mgKOH / g or less.
- the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
- the acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.
- the specific structure of the polymer dispersant having a quaternary ammonium base as a functional group is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as “repeating unit ( i) ").
- R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
- R 34 is a hydrogen atom or a methyl group.
- X is a divalent linking group
- Y ⁇ is a counter anion.
- the number of carbon atoms of the alkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 1 or more and preferably 10 or less. The following is more preferable.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms of the aryl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 6 or more and preferably 16 or less. The following is more preferable.
- Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
- a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
- the carbon number of the aralkyl group which may have a substituent in R 31 to R 33 in the above formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less. The following is more preferable.
- Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group.
- a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
- R 31 to R 33 are preferably each independently an alkyl group or an aralkyl group. Specifically, R 31 and R 33 are each independently a methyl group or an ethyl group. It is preferable that R 32 is a phenylmethylene group or a phenylethylene group, R 31 and R 33 are methyl groups, and R 32 is a phenylmethylene group.
- the polymer dispersant when it has a tertiary amine as a functional group, from the viewpoint of dispersibility, it may be a repeating unit represented by the following formula (ii) (hereinafter referred to as “repeating unit (ii)”) .).
- R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
- R 35 and R 36 may be bonded to each other to form a cyclic structure.
- R 37 is a hydrogen atom or a methyl group.
- Z is a divalent linking group.
- alkyl group which may have a substituent in R 35 and R 36 of the above formula (ii) those exemplified as R 31 to R 33 of the above formula (i) may be preferably employed. it can.
- aryl group which may have a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) should be preferably employed.
- aralkyl group optionally having a substituent in R 35 and R 36 in the above formula (ii) those exemplified as R 31 to R 33 in the above formula (i) may be preferably employed. it can.
- R 35 and R 36 are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
- alkyl group, aralkyl group or aryl group in R 31 to R 33 of the above formula (i) and R 35 and R 36 of the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, etc. are mentioned.
- examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, —COOR 44 — group (wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), etc. Is a —COO—R 44 — group.
- examples of Y ⁇ of the counter anion include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , PF 6 ⁇ and the like.
- the content rate of the repeating unit represented by the said formula (i) is not specifically limited, From a dispersible viewpoint, it is represented by the content rate of the repeating unit represented by the said formula (i), and the said formula (ii). Preferably it is 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, based on the total content of repeating units.
- the amount is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
- the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more from the viewpoint of dispersibility, and 5 mol. % Or more, more preferably 10 mol% or more, more preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. Is more preferable, and it is especially preferable that it is 15 mol% or less.
- the content ratio of the repeating unit represented by the formula (ii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more from the viewpoint of dispersibility. % Or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, more preferably 60 mol% or less, and 40 mol% or less. Is more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
- the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii)” from the viewpoint of improving compatibility with binder components such as a solvent and improving dispersion stability. It is preferable that it has.
- R 40 is an ethylene group or a propylene group
- R 41 is an alkyl group which may have a substituent
- R 42 is a hydrogen atom or a methyl group.
- n is an integer of 1 to 20.
- the number of carbon atoms of the alkyl group which may have a substituent in R 41 of the above formula (iii) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- n in the above formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoints of compatibility with a binder component such as a solvent and dispersibility. More preferably, it is 5 or less.
- the content ratio of the repeating unit represented by the formula (iii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. More preferably, it is 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
- the amount is within the above range, compatibility with a binder component such as a solvent tends to be compatible with dispersion stability.
- the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv)” from the viewpoint of improving the compatibility of the dispersing agent with a binder component such as a solvent and improving dispersion stability. ) ").).
- R 38 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
- R 39 is a hydrogen atom or a methyl group.
- the number of carbon atoms of the alkyl group that may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is preferably 10 or less, and more preferably 8 or less.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified.
- It is preferably a group, a pentyl group or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms of the aryl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is more preferably 8 or less.
- Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group.
- a phenyl group, a methylphenyl group, and an ethylphenyl group A dimethylphenyl group, or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group, or an ethylphenyl group.
- the carbon number of the aralkyl group which may have a substituent in R 38 in the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. More preferred is 10 or less.
- Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group.
- a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.
- R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group from the viewpoints of solvent compatibility and dispersion stability.
- the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
- the linear alkyl group represented by R 38 includes both linear and branched chains.
- the content of the repeating unit represented by the formula (iv) in all the repeating units of the polymer dispersant is preferably 30 mol% or more and 40 mol% or more from the viewpoint of dispersibility. More preferably, it is more preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less.
- the polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv).
- repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.
- the polymer dispersant is composed of an A block having the repeating unit (i) and the repeating unit (ii), and a B block not having the repeating unit (i) and the repeating unit (ii). It is preferable that it is a block copolymer which has these.
- the block copolymer is preferably an AB block copolymer or a BAB block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved.
- the B block preferably has a repeating unit (iii), and more preferably has a repeating unit (iv).
- the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization and block copolymerization.
- the repeating unit (i) and the repeating unit (ii) may be contained in two or more kinds in one A block. In that case, each repeating unit is randomly copolymerized in the A block. It may be contained in any form of block copolymerization.
- a repeating unit other than the repeating unit (i) and the repeating unit (ii) may be contained in the A block.
- Examples of such a repeating unit include the aforementioned (meth) acrylic acid ester-based unit.
- Examples include a repeating unit derived from a monomer.
- the content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
- Repeating units other than the repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (Meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonic acid Ether; repeating units derived from monomers such as N-methacryloylmorpholine.
- styrene monomers such as styrene and ⁇ -methylstyrene
- (Meth) acrylate monomers such as (meth) acrylic acid chloride
- (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide
- vinyl acetate acrylon
- the content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in the block.
- the dispersant is preferably used in combination with a pigment derivative described later.
- the (C) alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group.
- an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing resin is used.
- a urethane resin, a novolac resin, a polyvinylphenol resin, and the like can be given.
- an epoxy (meth) acrylate resin and an acrylic resin are preferable. These can be used individually by 1 type or in mixture of multiple types.
- the alkali-soluble resin used in the present invention is particularly excellent in the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). It is preferably used from the viewpoint of plate making.
- ⁇ Alkali-soluble resin (c1)> It was obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
- epoxy resin used as a raw material for example, bisphenol A type epoxy resin (for example, “Epicoat (registered trademark; the same applies hereinafter) 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Mitsubishi Chemical Corporation, etc. ), Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd.
- bisphenol A type epoxy resin for example, “Epicoat (registered trademark; the same applies hereinafter) 828
- Epoxy obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd.
- a represents an average value and represents a number from 0 to 10.
- R 111 represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group.
- a plurality of R 111 present in one molecule may be the same or different.
- R 121 represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group.
- a plurality of R 121 present in one molecule may be the same or different.
- X represents a linking group represented by the following general formula (C3-1) or (C3-2). However, one or more adamantane structures are included in the molecular structure.
- c represents an integer of 2 or 3.
- R 131 to R 134 and R 135 to R 137 are each independently an adamantyl group, a hydrogen atom, or a substituent which may have a substituent. And an alkyl group having 1 to 12 carbon atoms which may have a phenyl group which may have a substituent. * Indicates a bond.
- p and q each independently represent an integer of 0 to 4
- R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
- R 143 and R 144 each independently represents an alkylene group having 1 to 4 carbon atoms
- x and y each independently represents an integer of 0 or more.
- an epoxy resin represented by any one of the general formulas (C1) to (C4) it is preferable to use an epoxy resin represented by any one of the general formulas (C1) to (C4).
- Examples of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth) acryl
- an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
- a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
- an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can.
- esterification catalyst used here tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
- the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
- the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
- Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal
- examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
- maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof.
- Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
- a known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid having a carboxyl group to epoxy resin.
- the target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction.
- the addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 The degree is preferably in the range of ⁇ 140 mgKOH / g.
- the carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
- the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating.
- the polybasic acid and / or its anhydride Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the carboxyl group-containing epoxy (meth) acrylate resin is usually 1000 or more, preferably 1500 or more, and usually 10,000 or less, preferably 8000. Below, more preferably 6000 or less. If the weight average molecular weight is small, the solubility in the developer is high, and if it is too large, the solubility in the developer is low.
- the carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
- (C) alkali-soluble resin used by this invention may replace a part of above-mentioned carboxyl group-containing epoxy (meth) acrylate resin with another binder resin, unless the performance of this invention is impaired. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination.
- the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (C) alkali-soluble resin is preferably 50% by mass or more, particularly preferably 80% by mass or more.
- binder resins that can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin are not limited, and may be selected from resins that are usually used in photosensitive coloring compositions. Examples thereof include binder resins described in Japanese Patent Application Publication No. 2007-271727, Japanese Patent Application Publication No. 2007-316620, Japanese Patent Application Publication No. 2007-334290, and the like.
- binder resins may be used alone or in combination of two or more.
- the photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
- an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used. Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A No. 2000-56118.
- N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503; Radical activators such as -aryl- ⁇ -amino acid salts and N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750 And the oxime ester derivatives described in the above.
- titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny) 1-yl), dicyclopentadienyltitanium di (2,6-difluorophen-1-yl), dicyclopentadienyltitanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadieny
- Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.
- halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.
- halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.
- ⁇ -aminoalkylphenone derivatives include 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-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. It is
- oxime derivatives are particularly effective in terms of sensitivity and plate-making properties, and in the case of using an alkali-soluble resin containing a phenolic hydroxyl group, in terms of sensitivity.
- oxime derivatives oxime ester and ketoxime ester compounds
- excellent in sensitivity are useful.
- the oxime compound include a compound containing a structural moiety represented by the following general formula (3), and preferably include an oxime ester compound represented by the following general formula (3a).
- R 22 is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and 3 carbon atoms.
- R 21a represents a hydrogen atom 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 21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
- R 21a may form a ring together with R 21b , and the linking group may be a C 1-10 alkylene group 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 22a 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 3 carbon atoms.
- R 22 in the general formula (3) and R 22a in the general formula (3a) 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.
- R 21a in the general formula (3a) is preferably an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.
- R 21b in the general formula (3a) is preferably an optionally substituted carbazoyl group, an optionally substituted thioxanthonyl group, or an optionally substituted phenyl sulfide group.
- an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an amide group etc. are mentioned. It is done.
- Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.
- An oxime ester initiator having a carbazole group having a nitro group is also effective.
- the ketoxime compound include a compound containing a structural moiety represented by the following general formula (4), and preferably an oxime ester compound represented by the following general formula (5).
- R 24 has the same meaning as R 22 in Formula (3).
- each R 23a may be a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl having 1 to 20 carbon atoms.
- alkoxycarbonylalkyl group having 3 to 20 carbon atoms phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or heteroarylthio group
- R 23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
- R 23a may form a ring together with R 23b , 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 24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, and 7 carbon atoms.
- R 24 in the general formula (4) and R 24a 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 23a 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 23b in the general formula (5) is preferably an optionally substituted carbazoyl group or an optionally substituted phenyl sulfide group.
- ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.
- the photopolymerization initiator is preferably an oxime ester initiator and / or a ketoxime ester initiator.
- 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 photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass, preferably 0.5 to 10% by mass, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developability tends to be reduced, while if it is too small, the preferred colored cured product shape and step may not be formed.
- benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone
- Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, ⁇ -hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropyl
- oxime ester derivatives are particularly preferable from the viewpoint of sensitivity.
- oxime ester derivatives a photopolymerization initiator having a diphenyl sulfide skeleton is preferable from the viewpoint of solvent resistance.
- those represented by the following general formula (5-1) can be used.
- R 23a and R 24a have the same meaning as in the general formula (5).
- R 25a and R 25b each independently represent R 25c , OR 25c , CN, OH, or a halogen atom, f represents an integer of 0 to 5, and g represents an integer of 0 to 4.
- R 25c represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
- the hydrogen atom of the substituent represented by R 25c may be further substituted with a halogen atom, and the alkylene moiety of the substituent represented by R 25c is —O—, —S—, —COO—, —OCO.
- R 25d represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.
- the alkyl part of the substituent represented by R 25c may have a branched side chain, and may be cyclopentyl or cyclohexyl.
- R 26 represents OH, COOH or a group represented by the following general formula (5-2), and h represents an integer of 0 to 5.
- R 26a represents —O—, —S—, —OCO— or —COO—.
- R 26b represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or an arylene alkylene group having 7 to 30 carbon atoms.
- the alkylene part of the substituent represented by R 26b may be interrupted 1 to 5 times by —O—, —S—, —COO— or —OCO—.
- the alkylene part of the substituent represented by R 26b may have a branched side chain or cyclohexylene.
- R 26c represents OH or COOH, and i represents an integer of 1 to 3. * Indicates a bond.
- a photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
- a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
- sensitizing dyes xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335 are described.
- amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
- Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazol
- polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done.
- a polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
- photopolymerizable monomer In the photosensitive coloring composition of this invention, it is preferable from points, such as a sensitivity, that a photopolymerizable monomer (photopolymerizable compound) is further included.
- the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.
- polyfunctional ethylenic monomers having two or more ethylenically unsaturated groups in one molecule.
- polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
- ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.
- itaconic acid ester replaced by itaconate
- ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
- the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
- a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted.
- urethane (meth) acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical). These may be used alone or in combination of two or more.
- the photosensitive coloring composition of the present invention includes adhesion improvers such as organic solvents and silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, and surfactants.
- adhesion improvers such as organic solvents and silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, and surfactants.
- pigment derivatives and the like can be appropriately blended.
- the photosensitive coloring composition of the present invention is usually used as (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and as required.
- the photopolymerizable monomer and other various materials used are dissolved or dispersed in an organic solvent. It is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. A solvent having a boiling point of 120 to 280 ° C. is more preferable.
- organic solvents include the following. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl
- acetone Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones; Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentan
- Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxy
- solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve” is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name). These organic solvents may be used alone or in combination of two or more.
- the organic solvent has a boiling point in the range of 100 to 200 ° C. (under pressure of 101.25 [hPa]. Hereinafter, all of the boiling points are the same). It is preferable to select one. More preferably, it has a boiling point of 120 to 170 ° C.
- glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
- glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
- glycol monoalkyl ethers are particularly preferable.
- propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition.
- Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease.
- the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
- an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”).
- high boiling point solvent an organic solvent having a boiling point of 150 ° C. or higher
- the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation and solidification of a coloring material at the tip of the slit nozzle.
- diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred because of their high effects.
- the content of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying temperature of the composition will be slowed down. There is a concern that problems such as tact defects in the reduced-pressure drying process and pin marks of prebaking may be caused in the matrix manufacturing process.
- the high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
- Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
- the photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
- an adhesion improver a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
- the kind of the silane coupling agent various kinds such as epoxy, (meth) acrylic and amino can be used alone or in combination of two or more.
- Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- Epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Isocyanate silanes such as 3-isocyanatopropyltriethoxysilane are mentioned, and epoxy silane silane coupling agents are particularly preferable.
- the phosphoric acid group-containing compound (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.
- R 51 represents a hydrogen atom or a methyl group
- l and l ′ are integers of 1 to 10
- m is 1, 2 or 3.
- These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
- the photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.
- surfactant for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used.
- nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
- fluorine-based and silicon-based surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone).
- F-470, F-475, F-478, F-559 DIC
- SH7PA Toray Silicone
- DS-401 Daikin
- L-77 Long Term Evolution
- FC4430 manufactured by Sumitomo 3M
- 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
- the photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
- a pigment derivative as a dispersion aid
- As pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
- derivatives such as phthalocyanines and quinophthalones are preferable.
- Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
- pigment derivatives 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 may be used alone or in combination of two or more.
- Photoacid generator is a compound capable of generating an acid by ultraviolet rays, and has a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure. The crosslinking reaction will proceed.
- a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure.
- the crosslinking reaction will proceed.
- photoacid generators those having a high solubility in a solvent, particularly in a solvent used in a photosensitive coloring 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) triphen
- Crosslinking agent can be further added to the photosensitive coloring composition of the present invention.
- a melamine or guanamine compound can be used.
- these cross-linking agents include melamine or guanamine compounds represented by the following general formula (6).
- R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms
- R 61 represents R 62, R 63 , R 64 , R 65 one of R 66 and R 67
- R 61 represents R 62, R 63, one of R 64 and R 65 are -CH 2 oR 68 group in the case of an aryl group having 6 to 12 carbon atoms
- R 62 , R 63 , R 64 , R 65 , R 66 and R 67 independently of one another, represent hydrogen or a —CH 2 OR 68 group, wherein R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom, etc. May be bonded to each other.
- Each of the alkyl group and the alkoxy group may have about 1 to 6 carbon atoms.
- Alkyl group represented by R 68 is, among the above, methyl group or an ethyl group, especially a methyl group.
- Melamine compounds corresponding to the general formula (6) that is, compounds of the following general formula (6-1) include hexamethylol melamine, pentamethylol melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxy Methyl melamine, hexaethoxymethyl melamine and the like are included.
- R 62 , R 63 , R 64 , R 65 , R 66 and R 67 when one of R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is an aryl group, one of R 62 , R 63 , R 64 and R 65 is —CH 2.
- guanamine compounds corresponding to the general formula (6) that is, compounds in which R 61 in the general formula (6) is aryl include tetramethylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxymethyl benzoguanamine, tetraethoxymethyl benzoguanamine. Etc. are included.
- 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 of the crosslinking agent used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.
- Mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol (3-mercaptobutyrate), butanediol bis (3-mercapto
- the content of (A) the coloring material is usually preferably 10% by mass or more and 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. Usually, it is 50 mass% or less.
- the content ratio of the (A-1) organic black pigment to (A) 100% by mass of the color material is usually 10% by mass or more, preferably 30% by mass or more, and usually 100% by mass or less. If the content of the (A-1) organic black pigment in the color material (A) is too small, a sufficient optical density (OD) may not be obtained.
- the coloring material may contain (A-1) an organic black pigment and (A-2) an organic coloring pigment.
- the content ratio of (A-1) organic black pigment to 100% by mass of (A) color material is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 90% by mass.
- it is preferably 80% by mass or less, more preferably 60% by mass or less.
- the content of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass.
- it is 70 mass% or less more preferably.
- the content ratio of (A-1) organic black pigment to (A-2) 100 parts by weight of organic coloring pigment is usually 15 parts by weight or more, preferably 20 parts by weight or more, and usually 900 parts by weight or less, preferably 800 parts by weight. Part or less, more preferably 500 parts by weight or less, and still more preferably 200 parts by weight or less.
- the coloring material may contain (A-1) an organic black pigment and (A-3) carbon black.
- the content ratio of (A-1) organic black pigment to 100% by mass of (A) color material is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass.
- the content of (A-3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less.
- the content ratio of (A-1) organic black pigment to (A-3) 100 parts by mass of carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, usually 2000 parts by mass or less, preferably 1000 parts by mass. It is as follows.
- the (A) coloring material may contain (A-2) an organic coloring pigment and (A-3) carbon black together with (A-1) an organic black pigment. is there.
- the content ratio of (A-1) organic black pigment to 100% by mass of (A) color material is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less. It is.
- the content of the (A-2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less.
- the content of (A-3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less.
- the content ratio of (A-1) organic black pigment to 100 parts by mass of (A-2) organic color pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800 parts by mass or less, preferably 700 parts by mass. It is below mass parts.
- the content ratio of (A-1) organic black pigment to (A-3) 100 parts by mass of carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1000 parts by mass or less, preferably 900 parts by mass. It is as follows.
- (B) Content of a dispersing agent is 1 mass% or more normally in solid content of a photosensitive coloring composition, 3 mass% or more is preferable, 5 mass% or more is more preferable, and usually 30 mass% or less, 20 mass% or less is preferable and 15 mass% or less is especially preferable. Further, the content of the dispersant (B) with respect to 100% by mass of the (A) colorant is usually preferably 5% by mass or more and 10% by mass or more, and usually 50% by mass or less, particularly 30% by mass or less. preferable. (B) If the content of the dispersant is too small, sufficient dispersibility may not be obtained, and if it is too much, the proportion of other components may be relatively decreased, and sensitivity, plate-making property, etc. may be decreased. .
- (C) Content of alkali-soluble resin is 5 mass% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass% or more, Usually 85 mass% or less, Preferably 80% by mass or less.
- (D) Content of a photoinitiator is 0.1 mass% or more normally with respect to the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass% or more, More preferably, it is 1 mass. %, Usually 15% by mass or less, preferably 10% by mass or less.
- the content of the polymerization accelerator is preferably 0.05% by mass or more, and usually 0.05% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. 10% by mass or less, preferably 5% by mass or less, and the polymerization accelerator is usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D). It is preferable to use in proportion.
- the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.
- a photopolymerizable monomer When a photopolymerizable monomer is used, its content is usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the photosensitive coloring composition. When there is too much content of a photopolymerizable monomer, the permeability
- the minimum of content of a photopolymerizable monomer is 1 mass% or more normally, Preferably it is 5 mass% or more.
- an adhesion improver When an adhesion improver is used, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4%, based on the total solid content in the photosensitive coloring composition. ⁇ 2% by weight. If the content of the adhesion improver is less than the above range, the effect of improving the adhesion may not be sufficiently obtained. If the content is too large, the sensitivity may be lowered, or the residue may remain as a defect after development. .
- the content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0, based on the total solid content in the photosensitive coloring composition. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.
- the photosensitive coloring composition of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
- the photosensitive coloring composition of the present invention can be suitably used for forming a black matrix, and preferably exhibits a black color from such a viewpoint, and has an optical density (OD) per 1 ⁇ m film thickness of the coating film. It is preferable that it is 1.0 or more.
- the photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method. Usually, it is preferable to disperse (A) the color material in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant (A) is finely divided by the dispersion treatment, the resist coating characteristics are improved.
- the dispersion treatment is usually preferably carried out in a system in which (A) a color material, an organic solvent, (B) a dispersant, and (C) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as dispersion treatment).
- the mixture to be provided and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”).
- a polymer dispersant as the dispersant (B) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
- a pigment dispersion containing at least (A) a color material, an organic solvent, and (B) a dispersant.
- A) colorant, organic solvent, and (B) dispersant that can be used in the pigment dispersion those described as those that can be used in the photosensitive coloring composition can be preferably employed.
- a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
- the color material (A) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
- the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
- the dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus.
- the standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300.
- the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like.
- the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
- the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
- the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution.
- fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
- a cured product can be obtained by curing the photosensitive coloring composition of the present invention.
- a cured product obtained by curing the photosensitive coloring composition can be suitably used as a black matrix or a colored spacer.
- the support for forming the black matrix is not particularly limited as long as it has an appropriate strength.
- a transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.
- a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
- the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness.
- the thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
- the photosensitive coloring composition of the present invention is applied on a transparent substrate and dried, and then the photosensitive matrix is coated.
- a black mask is formed by placing a photomask on the coloring composition and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.
- the black matrix of the present invention is effective for forming on the TFT element substrate, but the configuration is not particularly limited in each of the COA and BOA systems, and can be applied to various configurations. .
- the photosensitive coloring composition for black matrix is applied on a transparent substrate by spinner method, wire bar method, flow coating method, die coating method. , Roll coating method or spray coating method.
- the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.
- the thickness of the coating film is usually preferably in the range of 0.2 to 10 ⁇ m, more preferably in the range of 0.5 to 6 ⁇ m, and still more preferably in the range of 1 to 4 ⁇ m, as the film thickness after drying. is there.
- the coating film after the photosensitive coloring composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
- the drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes. The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate.
- the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
- Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
- the light source used for said image exposure is not specifically 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 an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
- the black matrix according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after the coating film made of the photosensitive coloring composition is subjected to image exposure with the above light source.
- An image can be formed on a substrate by development using a film.
- This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
- Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
- Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
- Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
- surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
- nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
- anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters
- amphoteric surfactants such as alkylbetaines and amino acids.
- organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
- the organic solvent may be used alone or in combination with an aqueous solution.
- the development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly 15 to 45 ° C., particularly preferably 20 to 40 ° C.
- the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
- thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment.
- the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is in the range of 5 to 60 minutes.
- the line width of the black matrix formed as described above is usually 3 to 50 ⁇ m, preferably 4 to 30 ⁇ m, and the height is usually 0.5 to 5 ⁇ m, preferably 1 to 4 ⁇ m.
- the volume resistivity is 1 ⁇ 10 13 ⁇ ⁇ cm or more, preferably 1 ⁇ 10 14 ⁇ ⁇ cm or more, and the relative dielectric constant is 6 or less, preferably 5 or less, and usually 2 or more.
- the optical density (OD) per 1 ⁇ m thickness is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 4.0 or less.
- the optical density (OD) is a value measured by a method described later.
- the photosensitive coloring composition of this Embodiment can also be used as a resist for coloring spacers other than a black matrix.
- a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Application Laid-Open No. 8-234212.
- the publication discloses that the spacer is light-shielding.
- the colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.
- the image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL (Electro Luminesence) display described later.
- the liquid crystal display device of the present invention is manufactured using the above-described black matrix of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
- the black matrix of the present invention is provided on a TFT element substrate, red, green and blue pixels are formed, an overcoat layer is formed as necessary, and further, ITO and IZO are formed on the image.
- ITO and IZO are formed on the image.
- the transparent electrode may not be formed.
- a liquid crystal display device usually forms an alignment film on a color filter, and after dispersing spacers on the alignment film or forming a photo spacer, it is bonded to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the cell and connected to the counter electrode to complete.
- a resin film such as polyimide is suitable.
- a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm.
- the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.
- the black matrix of the present invention there is no particular limitation on the formation order and formation position of the color pixels and the black matrix.
- the spacer a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 ⁇ m is usually preferable.
- a photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
- the gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 ⁇ m.
- portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin.
- the sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
- the liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. .
- the degree of decompression in the liquid crystal cell is usually 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 7 Pa, preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 6 Pa. Further, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is usually 30 to 100 ° C., more preferably 50 to 90 ° C.
- the warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal.
- the liquid crystal cell into which the liquid crystal is injected is sealed with a UV curable resin in which the liquid crystal injection port is cured, thereby completing a liquid crystal display device (panel).
- liquid crystal there are no particular restrictions on the type of liquid crystal, and it is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like.
- thermotropic liquid crystal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, but any of them may be used.
- the organic EL display of the present invention can be produced using the black matrix of the present invention.
- a pattern that is, the pixel 20 and the adjacent one
- a color filter in which a black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic light-emitting body 500 is laminated on the color filter with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween.
- the organic EL element 100 can be produced.
- at least one of the pixel 20 and the black matrix is manufactured using the photosensitive coloring composition of the present invention.
- a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter.
- a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used.
- an organic EL display can be produced.
- the black matrix of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
- Organic black pigment Perylene black> Lumogen (registered trademark) Black FK4281 manufactured by BASF
- Organic black pigment aniline black> PALIOTOL (registered trademark) Black L0080, manufactured by BASF
- the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours.
- THPA tetrahydrophthalic anhydride
- the weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, and the acid value was 80 mgKOH / g.
- ⁇ Dispersant-II> "DISPERBYK-2000" manufactured by Big Chemie (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base)
- compound 1 (0.98 g, 5 mmol) and methylene chloride (17 mL) were added to a 50 mL three-necked flask. After cooling to 3 ° C., o-toluoyl chloride (0.77 g, 5 mmol) was added dropwise. To this, aluminum chloride (0.67 g, 5 mmol) was slowly added over 1 hour. After completion of the addition, the mixture was further stirred at 3 ° C. for 2 hours, and methylene chloride (8 mL) was added. Next, glutaric anhydride (0.68 g, 6 mmol) was added over 30 minutes, and then aluminum chloride (1.90 g, 14 mmol) was added over 30 minutes.
- compound 3 (1.00 g, 2.26 mmol) and methylene chloride (10 mL) were placed in a 50 mL three-necked flask and cooled to 10 ° C. To this was added 1N hydrogen chloride in diethyl ether (4.68 mL). Next, amyl nitrite (0.36 g, 3.04 mmol) was added and reacted at 10 ° C. for 4 hours. After adding water (10 mL), it wash
- ⁇ Preparation of pigment dispersions 1 to 7 The pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was obtained. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mm ⁇ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the completion of dispersion, the beads and dispersion were separated by a filter to prepare pigment dispersions 1 to 7.
- Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small amount of Na, Ca, and S was used, and a coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry.
- the slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Mitsubishi Chemical Corporation) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
- Examples 1 to 8 and Comparative Examples 1 to 4 Using the pigment dispersion and the coated carbon black dispersion prepared above, each component was added so that the ratio in the solid content was the mixing ratio shown in Table 2, and further PGMEA was added so that the solid content was 17% by mass. The mixture was stirred and dissolved to prepare a photosensitive coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid content was 40% by mass, and in Comparative Example 3, the pigment concentration in the solid content was 30% by mass.
- the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer is 3, the photopolymerization initiator is 4% by mass in the solid content, and the additive is 0.5% by mass and 0.1% by mass of the surfactant were used.
- the obtained photosensitive coloring composition it evaluated by the method mentioned later.
- the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2 ⁇ m, dried under reduced pressure for 1 minute, and then dried at 100 ° C. for 90 seconds with a hot plate.
- a resist-coated substrate (substrate-1) was obtained by heating at 230 ° C. for 30 minutes.
- the optical density (OD) of the obtained substrate was measured with a transmission densitometer Gretag Macbeth D200-II, and the film thickness was measured with a non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd. It was measured.
- Table 3 shows the optical density (OD) per 1 ⁇ m of film thickness.
- a substrate (substrate-2) was prepared in the same manner as in the method for preparing substrate-1, except that a glass substrate having a chromium vapor deposition film was used instead of the glass substrate.
- a gold counter electrode was formed on the resist coating film by vapor deposition.
- the relative dielectric constant at 1 kHz ⁇ 1 V was measured using “LCR meter 4284A” manufactured by HP (current Agilent). The results are shown in Table 3.
- Example 1 From a comparison between Example 1 and Comparative Examples 1, 2, and 4, it was confirmed that the substrate obtained from the photosensitive coloring composition of the present invention had a higher OD and a higher shielding property at the same pigment concentration. .
- Comparative Examples 1 and 2 a linear pattern was not obtained even after development for 10 minutes. This is because Comparative Examples 1 and 2 contain perylene black as a pigment, but it is necessary to use a large amount of dispersant when dispersing perylene black, which seems to have adversely affected the plate-making characteristics. The larger the line width, the higher the sensitivity. However, by using (A-1) the organic black pigment and (A-2) the organic coloring pigment together, the sensitivity can be improved without greatly reducing the OD. It was confirmed from Examples 4 and 5 that it could be increased.
- Comparative Example 3 shows that the pigment is only coated carbon black and exhibits a high OD, but the relative dielectric constant increases.
- Examples 6 and 7 show that the combination of (A-1) organic black pigment and (A-3) carbon black used in the present invention enables high OD and low dielectric constant. confirmed.
- Example 9 and Comparative Examples 5 to 7 Using the pigment dispersion prepared above, add each component so that the ratio in the solid content is the blending ratio in Table 5, and add PGMEA so that the solid content is 17% by mass, and stir and dissolve. A photosensitive coloring composition was prepared. Moreover, the viscosity was measured about each obtained photosensitive coloring composition by the Toki Sangyo Co., Ltd. RC80L type
- a basic polymer dispersant having a quaternary ammonium base and a basic polymer dispersant having no quaternary ammonium base are treated equally. It is known to show the same dispersibility.
- perylene black which is an organic black pigment, has no significant difference in the viscosity of the photosensitive coloring composition when using Dispersant I or Dispersant III. .
- Table 6 shows the viscosity values measured in the same manner as in Example 9 for the photosensitive coloring compositions of Examples 1 to 8.
- Example 6 in which (A-1) an organic black pigment and (A-3) carbon black were used in combination, (A-1) an organic black pigment and (A-2) an organic color pigment (A-3)
- the viscosity was the same as in Examples 1 and 2, and the pigment was uniformly dispersed in any of the photosensitive coloring compositions.
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Abstract
Description
最近では、カラー液晶表示素子のより高精細・高輝度化に対応するために、アクティブマトリクス型液晶ディスプレイにおいて、カラーフィルターをTFT素子基板側に設けたカラーフィルター・オン・アレイ方式(COA方式)やブラックマトリクスだけをTFT素子基板側に設けたブラックマトリクス・オン・アレイ方式(BOA方式)が提案されている。この方式によれば、カラーフィルター側にブラックマトリクスを形成する場合に比べ、アクティブ素子側との位置合わせマージンを取る必要がなくなるため、開口率を高くすることができ、その結果、高輝度化を図ることができる。 The black matrix for a liquid crystal display element is used to prevent light leakage from the drive electrodes in the liquid crystal display element. In general, a black matrix is a pattern of a light-shielding material in the form of stripes or lattices formed by using a photolithography method on a transparent substrate such as glass or plastic sheet that is paired with a TFT (Thin Film Transistor) element substrate. is there.
Recently, in order to cope with higher definition and higher brightness of color liquid crystal display elements, in an active matrix liquid crystal display, a color filter on array method (COA method) in which a color filter is provided on the TFT element substrate side, A black matrix on array method (BOA method) in which only the black matrix is provided on the TFT element substrate side has been proposed. According to this method, compared with the case where a black matrix is formed on the color filter side, it is not necessary to take an alignment margin with the active element side, so that the aperture ratio can be increased, and as a result, higher luminance can be achieved. You can plan.
このようなブラックマトリクスとしては、顔料に複数種の有機着色顔料とカーボンブラックを用いたブラックマトリクスが提案されている(例えば特許文献1参照)。 However, when such a structure is adopted, the black matrix has a volume resistivity above a certain level and a relative dielectric constant below a certain level so as not to cause a short circuit of an electric circuit even if it is directly mounted on a TFT element. Is required.
As such a black matrix, a black matrix using a plurality of types of organic coloring pigments and carbon black as a pigment has been proposed (for example, see Patent Document 1).
一方、有機顔料として、ビス-オキソジヒドロ-インドリレン-ベンゾフラン着色剤が知られている(例えば特許文献4参照)。本文献の中には該顔料をカラーフィルターの赤色層、青色層及び緑色層を形成するために用いることが記載されている。また、該顔料は電気泳動ディスプレイ用の有機黒色顔料としても用いられることが知られている(例えば特許文献5参照)。 In addition, photosensitive compositions for black matrix using organic black pigments as pigments are also known. Specifically, aniline black (for example, see Patent Document 2) and perylene black (for example, see Patent Document 3) are used. Known photosensitive compositions are known.
On the other hand, bis-oxodihydro-indolylene-benzofuran colorants are known as organic pigments (see, for example, Patent Document 4). This document describes that the pigment is used for forming a red layer, a blue layer and a green layer of a color filter. Moreover, it is known that this pigment is used also as an organic black pigment for electrophoretic displays (for example, refer patent document 5).
また、特許文献2や3に記載されている、前記アニリンブラックやペリレンブラックは、分散性が悪く、分散するために多くの分散剤を使用する必要があり、製版性等に問題が生じる場合があることがわかった。加えて遮蔽率(光学濃度)も十分なものではないことが分かった。 As a result of intensive studies by the present inventors, the photosensitive composition described in
In addition, the aniline black and perylene black described in Patent Documents 2 and 3 have poor dispersibility, and it is necessary to use a large amount of a dispersant to disperse, which may cause problems in plate-making properties. I found out. In addition, it was found that the shielding rate (optical density) was not sufficient.
本発明は、上記従来の実情に鑑みてなされたものであって、遮光性に優れ、しかも、分散性や製版性に優れ、十分に低い比誘電率を示す感光性着色組成物を提供することを目的とする。 Further, Patent Documents 4 and 5 have no description or suggestion about using a bis-oxodihydro-indoleylene-benzofuran colorant as a shielding agent used in an image display device, and when used as a shielding agent used in an image display device. The characteristics such as the optical density, dispersibility and plate-making property are also unknown.
The present invention has been made in view of the above-described conventional circumstances, and provides a photosensitive coloring composition having excellent light-shielding properties, excellent dispersibility and plate making properties, and exhibiting a sufficiently low relative dielectric constant. With the goal.
すなわち、本発明は以下の[1]~[17]の構成を有する。
[1](A)色材、(B)分散剤、(C)アルカリ可溶性樹脂、及び(D)光重合開始剤を少なくとも含有する感光性着色組成物であって、前記(A)色材が(A-1)下記一般式(1)で表される化合物、その幾何異性体、その塩、またはその幾何異性体の塩である有機黒色顔料を含み、かつ、前記(B)分散剤が4級アンモニウム塩基を官能基として有する高分子分散剤を含む感光性着色組成物。 As a result of intensive studies by the present inventors to solve the above-mentioned problems, the organic coloring pigment having a specific structure is used as the coloring material in the photosensitive coloring composition, and a specific dispersant is used. Thus, the inventors have found that the above problems can be solved, and have reached the present invention.
That is, the present invention has the following configurations [1] to [17].
[1] A photosensitive coloring composition containing at least (A) a coloring material, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein (A) the coloring material is (A-1) an organic black pigment that is a compound represented by the following general formula (1), a geometric isomer, a salt thereof, or a salt of the geometric isomer, and the dispersant (B) is 4 A photosensitive coloring composition comprising a polymer dispersant having a quaternary ammonium base as a functional group.
式中、R2、R4、R5、R7、R9およびR10は互いに独立して水素原子、フッ素原子または塩素原子であり、R3およびR8は互いに独立して水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3HまたはSO3 -であり、R1はR6と同一であり、R2はR7と同一であり、R3はR8と同一であり、R4はR9と同一であり、R5はR10と同一である、[1]に記載の感光性着色組成物。
[3]前記高分子分散剤が、さらに3級アミンを官能基として有する、[1]又は[2]に記載の感光性着色組成物。 [2] In the general formula (1),
In the formula, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom, and R 3 and R 8 are each independently a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , R 1 is the same as R 6 , R 2 is the same as R 7 , R 3 is the same as R 8 , The photosensitive coloring composition according to [1], wherein R 4 is the same as R 9 and R 5 is the same as R 10 .
[3] The photosensitive coloring composition according to [1] or [2], wherein the polymer dispersant further has a tertiary amine as a functional group.
<アルカリ可溶性樹脂(c1)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、多塩基酸及び/又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
<アルカリ可溶性樹脂(c2)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、並びに多塩基酸及び/又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 [4] The photosensitivity according to any one of [1] to [3], wherein the (C) alkali-soluble resin includes at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2). Coloring composition.
<Alkali-soluble resin (c1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.
[6](A-2)有機着色顔料が、以下の顔料のうち少なくとも1種を含有する、[5]に記載の感光性着色組成物。
青:カラーインデックスピグメントブルー60、又は15:6
赤:カラーインデックスピグメントレッド177、254、又は272
紫:カラーインデックスピグメントバイオレット23、又は29
橙:カラーインデックスピグメントオレンジ43、64、又は72
[7](A)色材100質量%に対する、前記(A-1)有機黒色顔料の含有割合が30~90質量%、(A-2)有機着色顔料の含有割合が10~70質量%である、[5]または[6]に記載の感光性着色組成物。
[8](A)色材がさらに(A-3)カーボンブラックを含有する、[1]~[7]のいずれか1つに記載の感光性着色組成物。
[9](A)色材100質量%に対する、前記(A-1)有機黒色顔料の含有割合が50~90質量%、(A-3)カーボンブラックの含有割合が10~50質量%である、[8]に記載の感光性着色組成物。 [5] The photosensitive coloring composition according to any one of [1] to [4], wherein the (A) coloring material further contains (A-2) an organic coloring pigment.
[6] The photosensitive coloring composition according to [5], wherein the (A-2) organic coloring pigment contains at least one of the following pigments.
Blue: Color index pigment blue 60 or 15: 6
Red: Color index pigment red 177, 254, or 272
Purple: Color Index Pigment Violet 23 or 29
Orange: Color index pigment orange 43, 64, or 72
[7] The content ratio of the (A-1) organic black pigment is 30 to 90 mass% and the content ratio of the (A-2) organic color pigment is 10 to 70 mass% with respect to 100 mass% of the color material (A). The photosensitive coloring composition as described in [5] or [6].
[8] The photosensitive coloring composition according to any one of [1] to [7], wherein the (A) coloring material further contains (A-3) carbon black.
[9] The content ratio of the (A-1) organic black pigment is 50 to 90 mass% and the content ratio of (A-3) carbon black is 10 to 50 mass% with respect to 100 mass% of the color material (A). The photosensitive coloring composition as described in [8].
[11][1]~[10]のいずれか1つに記載の感光性着色組成物を硬化して得られる硬化物。
[12][11]に記載の硬化物から形成されるブラックマトリクス。
[13][11]に記載の硬化物から形成される着色スペーサー。
[14][12]に記載のブラックマトリクス又は[13]に記載の着色スペーサーを含む画像表示装置。
[15](A)色材、及び(B)分散剤を含有する顔料分散液であって、前記(A)色材が(A-1)下記一般式(1)で表される化合物、その幾何異性体、その塩、またはその幾何異性体の塩である有機黒色顔料を含み、かつ、前記(B)分散剤が4級アンモニウム塩基を官能基として有する高分子分散剤を含む顔料分散液。 [10] The photosensitive coloring composition according to any one of [1] to [9], wherein (D) the photopolymerization initiator is an oxime ester initiator and / or a ketoxime ester initiator.
[11] A cured product obtained by curing the photosensitive coloring composition according to any one of [1] to [10].
[12] A black matrix formed from the cured product according to [11].
[13] A colored spacer formed from the cured product according to [11].
[14] An image display device comprising the black matrix according to [12] or the colored spacer according to [13].
[15] A pigment dispersion containing (A) a colorant and (B) a dispersant, wherein the (A) colorant is (A-1) a compound represented by the following general formula (1), A pigment dispersion containing an organic black pigment which is a geometric isomer, a salt thereof, or a salt of the geometric isomer, and wherein the (B) dispersant includes a polymer dispersant having a quaternary ammonium base as a functional group.
式中、R2、R4、R5、R7、R9およびR10は互いに独立して水素原子、フッ素原子、または塩素原子であり、R3およびR8は互いに独立して水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3HまたはSO3 -であり、R1はR6と同一であり、R2はR7と同一であり、R3はR8と同一であり、R4はR9と同一であり、R5はR10と同一である、[15]に記載の顔料分散液。
[17]前記高分子分散剤が、さらに3級アミンを官能基として有する、[15]又は[16]に記載の顔料分散液。 [16] In the general formula (1),
In the formula, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom, and R 3 and R 8 are independently a hydrogen atom, NO 2, OCH 3, OC 2 H 5, a bromine atom, a chlorine atom, CH 3, C 2 H 5 , N (CH 3) 2, N (CH 3) (C 2 H 5), N (C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , R 1 is the same as R 6 , R 2 is the same as R 7 , and R 3 is the same as R 8 , R 4 is the same as R 9 and R 5 is the same as R 10 .
[17] The pigment dispersion according to [15] or [16], wherein the polymer dispersant further has a tertiary amine as a functional group.
なお、本発明において、「(メタ)アクリル」とは「アクリル及び/又はメタクリル」を意味し、「(メタ)アクリレート」、「(メタ)アクリロイル」についても同様である。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.
本発明において「全固形分」とは、感光性着色組成物中又は後述するインク中に含まれる、溶剤以外の全成分を意味するものとする。
本発明において、重量平均分子量とは、GPC(ゲルパーミエーションクロマトグラフィー)によるポリスチレン換算の重量平均分子量(Mw)をさす。
また、本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分1gあたりの塩基量と当量のKOHの質量で表される値である。なお、測定方法については後述する。一方、「酸価」とは、特に断りのない限り有効固形分換算の酸価を表し、中和滴定により算出される。 In the present invention, the term “monomer” is a term corresponding to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, etc. in addition to a monomer (monomer) in a narrow sense. It is.
In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
本発明の感光性着色組成物(以下、「感光性着色組成物」又は「着色樹脂組成物」と称す場合がある)は、
(A)色材
(B)分散剤
(C)アルカリ可溶性樹脂
(D)光重合開始剤
を必須成分として含有し、必要に応じて、更に有機溶剤、シランカップリング剤等の密着向上剤、塗布性向上剤、現像改良剤、紫外線吸収剤、酸化防止剤、界面活性剤、顔料誘導体等、その他の配合成分を含むものであり、通常、各配合成分が、有機溶剤に溶解又は分散した状態で使用される。 [Photosensitive coloring composition]
The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “photosensitive coloring composition” or “colored resin composition”)
(A) Colorant (B) Dispersant (C) Alkali-soluble resin (D) Photopolymerization initiator is contained as an essential component, and if necessary, adhesion improvers such as organic solvents and silane coupling agents, coating It contains other compounding components such as property improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc., and each compounding component is usually dissolved or dispersed in an organic solvent. used.
本発明で用いる(A)色材は、(A-1)下記一般式(1)で表される化合物、その幾何異性体、その塩、またはその幾何異性体の塩である有機黒色顔料を含む。 <(A) Color material>
The coloring material (A) used in the present invention includes (A-1) a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or an organic black pigment that is a salt of the geometric isomer. .
R2、R3、R4、R5、R7、R8、R9およびR10は他の全てから互いに独立して水素原子、ハロゲン原子、R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N=CH2、N=CHR11、N=CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11またはSO2NR11R12である;
且つ、R2とR3、R3とR4、R4とR5、R7とR8、R8とR9、及びR9とR10からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、または酸素原子、硫黄原子、NH若しくはNR11ブリッジによって互いに結合することもできる;
R11およびR12は互いに独立して、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基または炭素数2~12のアルキニル基である。]
一般式(1)で表される化合物の幾何異性体は、以下のコア構造を有し(ただし、構造式中の置換基は省略している)、トランス-トランス異性体は恐らく最も安定である。 [In formula (1), R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 10 are independently of each other from a hydrogen atom, a halogen atom, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N = CH 2 , N = CHR 11 , N = CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , SO 2 NHR 11 or SO 2 NR 11 R 12 ;
And at least one combination selected from the group consisting of R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and R 9 and R 10 , Can also be bonded directly to each other or to each other by oxygen, sulfur, NH or NR 11 bridges;
R 11 and R 12 are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or carbon It is an alkynyl group of the number 2-12. ]
The geometric isomer of the compound represented by the general formula (1) has the following core structure (however, the substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable. .
R2、R4、R5、R7、R9およびR10は互いに独立して好ましくは水素原子、フッ素原子、または塩素原子であり、さらに好ましくは水素原子である。
R3およびR8は互いに独立して好ましくは水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3HまたはSO3 -であり、さらに好ましくは水素原子またはSO3Hである。 In the substituents of the general formula (1) and their definitions, the following is preferable because the shielding ratio tends to be high. This is because the following substituents are considered not to absorb and affect the hue of the pigment.
R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are independently of each other preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R 3 and R 8 are preferably independently of each other a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , more preferably a hydrogen atom or SO 3 H.
好ましくは、R1とR6、R2とR7、R3とR8、R4とR9、およびR5とR10からなる群から選ばれる少なくとも1つの組み合わせが同一であり、より好ましくは、R1はR6と同一であり、R2はR7と同一であり、R3はR8と同一であり、R4はR9と同一であり、かつ、R5はR10と同一である。 R 1 and R 6 are preferably each independently a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R 1 and R 6 , R 2 and R 7 , R 3 and R 8 , R 4 and R 9 , and R 5 and R 10 is the same, and more preferably R 1 is the same as R 6 , R 2 is the same as R 7 , R 3 is the same as R 8 , R 4 is the same as R 9 , and R 5 is the same as R 10 Are the same.
(A-1)の有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。また、分散の際に前記一般式(2)のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合がある。 Specific examples of such organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
The organic black pigment (A-1) is preferably used after being dispersed by a dispersant, a solvent and a method described later. In addition, when the sulfonic acid derivative of the general formula (2) is present during dispersion, dispersibility and storage stability may be improved.
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、更に好ましくはC.I.ピグメントレッド177、209、224、254を挙げることができる。なお、分散性や遮光性の点で、C.I.ピグメントレッド177、254、272を用いることが好ましく、本発明の感光性着色組成物を紫外線で硬化させる場合には、赤色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはC.I.ピグメントレッド254,272を用いることがより好ましい。 Specific examples of pigments that can be used in the present invention are shown by pigment numbers below. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 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. In terms of dispersibility and light shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used. When the photosensitive coloring composition of the present invention is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorptivity. Is C.I. I. It is more preferable to use CI Pigment Red 254,272.
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、更に好ましくは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。 Examples of green pigments include C.I. I.
Examples of yellow pigments include 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.
青:カラーインデックスピグメントブルー60、又は15:6
赤:カラーインデックスピグメントレッド177、254、又は272
紫:カラーインデックスピグメントバイオレット23又は29
橙:カラーインデックスピグメントオレンジ43、64又は72
なお、異なる色の顔料を組み合わせて用いる場合、色の組み合わせについては特に限定されないが、遮光性の観点からは例えば、赤色顔料と青色顔料の組み合わせ、又は、青色顔料とオレンジ顔料と紫色顔料の組み合わせなどが挙げられる。 Among these, it is preferable to contain at least one of the following pigments.
Blue: Color index pigment blue 60 or 15: 6
Red: Color index pigment red 177, 254, or 272
Purple: Color index pigment violet 23 or 29
Orange: Color index pigment orange 43, 64 or 72
In addition, when using different color pigments in combination, the color combination is not particularly limited, but from the viewpoint of light shielding properties, for example, a combination of a red pigment and a blue pigment, or a combination of a blue pigment, an orange pigment and a purple pigment Etc.
アゾ系染料としては、例えば、C.I.アシッドイエロー11、C.I.アシッドオレンジ7、C.I.アシッドレッド37、C.I.アシッドレッド180、C.I.アシッドブルー29、C.I.ダイレクトレッド28、C.I.ダイレクトレッド83、C.I.ダイレクトイエロー12、C.I.ダイレクトオレンジ26、C.I.ダイレクトグリーン28、C.I.ダイレクトグリーン59、C.I.リアクティブイエロー2、C.I.リアクティブレッド17、C.I.リアクティブレッド120、C.I.リアクティブブラック5、C.I.ディスパースオレンジ5、C.I.ディスパースレッド58、C.I.ディスパースブルー165、C.I.ベーシックブルー41、C.I.ベーシックレッド18、C.I.モルダントレッド7、C.I.モルダントイエロー5、C.I.モルダントブラック7等が挙げられる。 Further, a dye may be used in place of (A-2) the organic color pigment, and a dye may be used in addition to (A-2) the organic color pigment. Examples of the dye that can be used as the color material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.
この他、フタロシアニン系染料として、例えば、C.I.パッドブルー5等が、キノンイミン系染料として、例えば、C.I.ベーシックブルー3、C.I.ベーシックブルー9等が、キノリン系染料として、例えば、C.I.ソルベントイエロー33、C.I.アシッドイエロー3、C.I.ディスパースイエロー64等が、ニトロ系染料として、例えば、C.I.アシッドイエロー1、C.I.アシッドオレンジ3、C.I.ディスパースイエロー42等が挙げられる。 Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I.
Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I.
黒色色材を調製するために混合使用可能な色材としては、ビクトリアピュアブルー(42595)、オーラミンO(41000)、カチロンブリリアントフラビン(ベーシック13)、ローダミン6GCP(45160)、ローダミンB(45170)、サフラニンOK70:100(50240)、エリオグラウシンX(42080)、No.120/リオノールイエロー(21090)、リオノールイエローGRO(21090)、シムラーファーストイエロー8GF(21105)、ベンジジンイエロー4T-564D(21095)、シムラーファーストレッド4015(12355)、リオノールレッド7B4401(15850)、ファーストゲンブルーTGR-L(74160)、リオノールブルーSM(26150)、リオノールブルーES(ピグメントブルー15:6)、リオノーゲンレッドGD(ピグメントレッド168)、リオノールグリーン2YS(ピグメントグリーン36)等が挙げられる(なお、上記の( )内の数字は、カラーインデックス(C.I.)を意味する)。 In addition, a black pigment other than (A-1) can also be used in the photosensitive coloring composition of the present invention. Black pigments other than (A-1) may be used singly or as a mixture of red, green, blue and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.
Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).
また、(A-1)有機黒色顔料以外の色材として(A-3)カーボンブラックが遮光率、画像特性の観点から好ましく使用される。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 Examples of the black color material that can be used alone include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black.
In addition, (A-3) carbon black is preferably used as a color material other than the (A-1) organic black pigment from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.
デグサ社製:Printex(登録商標。以下同じ。)3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
キャボット社製:Monarch(登録商標。以下同じ。)120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL(登録商標。以下同じ。)99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN(登録商標。以下同じ。) XC72R、ELFTEX(登録商標)-8
コロンビヤン カーボン社製:RAVEN(登録商標。以下同じ。)11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000
カーボンブラックは、樹脂で被覆されたものを使用しても構わない。樹脂で被覆されたカーボンブラックを使用すると、ガラス基板への密着性や体積抵抗値を向上させる効果がある。樹脂で被覆されたカーボンブラックとしては、例えば日本国特開平09-71733号公報に記載されているカーボンブラック等が好適に使用できる。 Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, PrintP85, PrintP85, PrintP85 U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBl4, ck FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same shall apply hereinafter) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (99, REGAL 99) REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark; the same shall apply hereinafter) XC72R, ELFTEX (registered trademark) -8
Made by Colombian Carbon: RAVEN (registered trademark; the same applies hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA10850RA, RA10850RA, RA40850RA RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
Carbon black coated with a resin may be used. Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance. As the carbon black coated with the resin, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
具体的な合成樹脂としては、フェノール樹脂、メラミン樹脂、キシレン樹脂、ジアリルフタレート樹脂、グリプタル樹脂、エポキシ樹脂、アルキルベンゼン樹脂等の熱硬化性樹脂や、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、変性ポリフェニレンオキサイド、ポリスルフォン、ポリパラフェニレンテレフタルアミド、ポリアミドイミド、ポリイミド、ポリアミノビスマレイミド、ポリエーテルスルフォポリフェニレンスルフォン、ポリアリレート、ポリエーテルエーテルケトン、等の熱可塑性樹脂が使用できる。カーボンブラックに対する樹脂の被覆量は、カーボンブラックと樹脂の合計量に対し1~30質量%が好ましく、1質量%未満の量では、未処理のカーボンブラックと同様の分散性や分散安定性しか得られないおそれがある。一方、30質量%を超えると、樹脂同士の粘着性が強く、団子状の固まりとなり、分散が進まなくなるおそれがある。 The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure have a stronger function as amphoteric surfactants. From the viewpoint of dispersibility and dispersion stability, it is preferable.
Specific synthetic resins include phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin and other thermosetting resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and when the amount is less than 1% by mass, only dispersibility and dispersion stability similar to those of the untreated carbon black can be obtained. There is a risk of not being able to. On the other hand, when it exceeds 30% by mass, the adhesiveness between the resins is strong, and it becomes a dumpling-like mass, and the dispersion may not proceed.
これら各種の顔料は、複数種を併用することもできる。例えば、色度の調整のために、緑色顔料と黄色顔料とを併用したり、青色顔料と紫色顔料とを併用することができる。
これら各種顔料のうち(A-2)有機着色顔料として、遮光性の点で特に好ましく用いられる顔料としては、C.I.ピグメントブルー60、C.I.ピグメントブルー15:6、C.I.ピグメントレッド177、C.I.ピグメントレッド242、C.I.ピグメントブルー254、C.I.ピグメントバイオレット23、C.I.ピグメントバイオレット29、C.I.ピグメントオレンジ49、C.I.ピグメントオレンジ64、C.I.ピグメントオレンジ79が挙げられる。(A-2)有機着色顔料を含む場合、上記顔料のうち少なくとも1種以上を含有することが好ましく、2種以上を含有することが更に好ましい。 In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.
These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
Among these various pigments, (A-2) as organic coloring pigments, pigments particularly preferably used in terms of light shielding properties include C.I. I. Pigment blue 60, C.I. I. Pigment blue 15: 6, C.I. I. Pigment red 177, C.I. I. Pigment red 242, C.I. I. Pigment blue 254, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment orange 49, C.I. I. Pigment orange 64, C.I. I. Pigment orange 79. (A-2) When an organic coloring pigment is included, it preferably contains at least one of the above pigments, and more preferably contains two or more.
これらの顔料は、平均粒径が通常1μm以下、好ましくは0.5μm以下、更に好ましくは0.25μm以下となるよう、分散して用いることが好ましい。ここで平均粒径の基準は顔料粒子の数である。
なお、本発明において、顔料の平均粒径は、動的光散乱(DLS)により測定された顔料粒径から求めた値である。粒径測定は、十分に希釈された着色樹脂組成物(通常は希釈して、顔料濃度0.005~0.2質量%程度に調製。但し測定機器により推奨された濃度があれば、その濃度に従う)に対して行い、25℃にて測定する。 As (A-3) carbon black, resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
These pigments are preferably used dispersed in such a manner that the average particle size is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard of the average particle diameter is the number of pigment particles.
In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering (DLS). For particle size measurement, a fully diluted colored resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, its concentration And measure at 25 ° C.
本発明の感光性着色組成物においては、(A)色材を微細に分散させ、且つその分散状態を安定化させることが品質の安定性確保には重要なため、(B)分散剤を含み、特に、(A-1)有機黒色顔料の分散性の観点から、4級アンモニウム塩基を官能基として有する高分子分散剤を含む。
前記高分子分散剤は更に、分散安定性の面からカルボキシル基;リン酸基;スルホン酸基;又はこれらの塩基;一級、二級又は三級アミノ基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を更に有するものであってもよい。中でも特に、一級、二級又は三級アミノ基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を更に有する高分子分散剤が顔料を分散する際に少量の分散剤で分散することができるとの観点から好ましい。
これらの中でも、(A-1)有機黒色顔料の分散性の観点から、また、(A-2)有機着色顔料及び/又は(A-3)カーボンブラックの分散性の観点から、4級アンモニウム塩基及び3級アミノ基を官能基として有する高分子分散剤が好ましい。 <(B) Dispersant>
In the photosensitive coloring composition of the present invention, (A) it is important to finely disperse the coloring material and stabilize the dispersion state, so that it is important to ensure the stability of the quality. In particular, (A-1) from the viewpoint of dispersibility of the organic black pigment, a polymer dispersant having a quaternary ammonium base as a functional group is included.
From the viewpoint of dispersion stability, the polymer dispersant further includes a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary, or tertiary amino group; a nitrogen-containing heterogeneous group such as pyridine, pyrimidine, and pyrazine. It may further have a functional group such as a ring-derived group. Among them, a polymer dispersant further having a basic functional group such as a primary, secondary or tertiary amino group; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, etc. It is preferable from a viewpoint that it can disperse | distribute with a dispersing agent.
Among these, (A-1) from the viewpoint of dispersibility of the organic black pigment, and (A-2) from the viewpoint of dispersibility of the organic color pigment and / or (A-3) carbon black, a quaternary ammonium base. And a polymer dispersant having a tertiary amino group as a functional group is preferred.
これらの高分子分散剤は1種を単独で使用してもよく、又は2種以上を併用してもよい。 Specific examples of such a dispersant are trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like.
These polymer dispersants may be used alone or in combination of two or more.
これらの内、密着性及び直線性の面から、(B)分散剤は官能基を有するウレタン系高分子分散剤及び/又はアクリル系高分子分散剤を含むことが好ましく、アクリル系高分子分散剤を含むことが特に好ましい。
また分散性、保存性の面から、塩基性官能基を有し、ポリエステル結合及び/又はポリエーテル結合を有する高分子分散剤が好ましい。 The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of adhesion and linearity, (B) the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group, and an acrylic polymer dispersant. It is particularly preferable that
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester bond and / or a polyether bond is preferable.
ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を1個又は2個有する数平均分子量300~10,000の化合物と、同一分子内に活性水素と3級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量1,000~200,000の分散樹脂等が挙げられる。これらをベンジルクロリド等の四級化剤で処理することで、3級アミノ基の全部又は一部を4級アンモニウム塩基にすることができる。 Examples of the urethane and acrylic polymer dispersants include DISPERBYK 160 to 166, 182 series (both are urethane), DISPERBYK2000, 2001, LPN21116, etc. (both are acrylic) (all manufactured by Big Chemie).
Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, the same as a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000. Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.
ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら2種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン-プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの2種以上の混合物が挙げられる。 Examples of the compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. A mixture of two or more of the above.
これらは1種を単独で用いてもよく、2種以上を併用してもよい。 Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Is mentioned.
These may be used alone or in combination of two or more.
活性水素、即ち、酸素原子、窒素原子又は硫黄原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に1級のアミノ基の水素原子が好ましい。 A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
このような同一分子内に活性水素と3級アミノ基を有する化合物を例示するならば、N,N-ジメチル-1,3-プロパンジアミン、N,N-ジエチル-1,3-プロパンジアミン、N,N-ジプロピル-1,3-プロパンジアミン、N,N-ジブチル-1,3-プロパンジアミン、N,N-ジメチルエチレンジアミン、N,N-ジエチルエチレンジアミン、N,N-ジプロピルエチレンジアミン、N,N-ジブチルエチレンジアミン、N,N-ジメチル-1,4-ブタンジアミン、N,N-ジエチル-1,4-ブタンジアミン、N,N-ジプロピル-1,4-ブタンジアミン、N,N-ジブチル-1,4-ブタンジアミン等が挙げられる。 The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.
これらは1種を単独で用いてもよく、2種以上を併用してもよい。 Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among these, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, and 3-amino-1,2,4-triazole preferable.
These may be used alone or in combination of two or more.
ウレタン系高分子分散剤の重量平均分子量(Mw)は通常1,000~200,000、好ましくは2,000~100,000、より好ましくは3,000~50,000の範囲である。この分子量が1,000未満では分散性及び分散安定性が劣り、200,000を超えると溶解性が低下し分散性が劣ると同時に反応の制御が困難となる。 In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.
該A-B又はB-A-Bブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
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り、このうち、アニオンリビング重合法は、重合活性種がアニオンであり、例えば下記スキームで表される。 The B block is composed of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but a partial structure derived from two or more types of monomers is contained in one B block. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.
また、本発明で用いることができるA-Bブロック共重合体、B-A-Bブロック共重合体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。 The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer. / B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio). Outside this range, good heat resistance and dispersibility cannot be achieved. There is.
In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. Outside the range, it may not be possible to combine good heat resistance and dispersibility.
ここで、これらのブロック共重合体等の分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分1gあたりの塩基量と当量のKOHの質量で表し、次の方法により測定する。
100mLのビーカーに分散剤試料の0.5~1.5gを精秤し、50mLの酢酸で溶解する。pH電極を備えた自動滴定装置を使って、この溶液を0.1mol/LのHClO4酢酸溶液にて中和滴定する。滴定pH曲線の変曲点を滴定終点とし次式によりアミン価を求める。 Such a block copolymer usually contains an amino group generated in the production process, but its amine value is about 1 to 100 mgKOH / g, and from the viewpoint of dispersibility, Preferably it is 10 mgKOH / g or more, More preferably, it is 30 mgKOH / g or more, More preferably, it is 50 mgKOH / g or more, Preferably it is 90 mgKOH / g or less, More preferably, it is 80 mgKOH / g or less, More preferably, it is 75 mgKOH / g or less.
Here, the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.
〔但し、W:分散剤試料秤取量[g]、V:滴定終点での滴定量[mL]、S:分散剤試料の固形分濃度[質量%]を表す。〕
また、この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10mgKOH/g以下であり、その重量平均分子量(Mw)は、1000~100,000の範囲が好ましい。ブロック共重合体の重量平均分子量が1000未満であると分散安定性が低下する傾向があり、100,000を超えると現像性、解像性が低下する傾向にある。 Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.
同様に、上記式(ii)のR35及びR36における、置換基を有していてもよいアリール基としては、上記式(i)のR31~R33として例示したものを好ましく採用することができる。また、上記式(ii)のR35及びR36における、置換基を有していてもよいアラルキル基としては、上記式(i)のR31~R33として例示したものを好ましく採用することができる。 In addition, as the alkyl group which may have a substituent in R 35 and R 36 of the above formula (ii), those exemplified as R 31 to R 33 of the above formula (i) may be preferably employed. it can.
Similarly, as the aryl group which may have a substituent in R 35 and R 36 in the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) should be preferably employed. Can do. As the aralkyl group optionally having a substituent in R 35 and R 36 in the above formula (ii), those exemplified as R 31 to R 33 in the above formula (i) may be preferably employed. it can.
また、上記式(i)において、対アニオンのY-としては、Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -等が挙げられる。 In the above formulas (i) and (ii), examples of the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, —COOR 44 — group (wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), etc. Is a —COO—R 44 — group.
In the above formula (i), examples of Y − of the counter anion include Cl − , Br − , I − , ClO 4 − , BF 4 − , CH 3 COO − , PF 6 − and the like.
R38における、アルキル基が有していてもよい置換基としては、ハロゲン原子、アルコキシ基等が挙げられる。また、アリール基又はアラルキル基が有していてもよい置換基としては、鎖状のアルキル基、ハロゲン原子、アルコキシ基等が挙げられる。また、R38で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。 Among these, R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group from the viewpoints of solvent compatibility and dispersion stability.
In R 38, a substituent which may have an alkyl group, a halogen atom, an alkoxy group, and the like. Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. Further, the linear alkyl group represented by R 38 includes both linear and branched chains.
本発明で用いる(C)アルカリ可溶性樹脂としては、カルボキシル基又は水酸基を含む樹脂であれば特に限定はなく、例えばエポキシ(メタ)アクリレート系樹脂、アクリル系樹脂、カルボキシル基含有エポキシ樹脂、カルボキシル基含有ウレタン樹脂、ノボラック系樹脂、ポリビニルフェノール系樹脂等が挙げられるが、中でもエポキシ(メタ)アクリレート系樹脂、アクリル系樹脂が好ましい。これらは1種を単独で、或いは複数種を混合して使用することができる。 <(C) Alkali-soluble resin>
The (C) alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group. For example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, a carboxyl group-containing resin is used. A urethane resin, a novolac resin, a polyvinylphenol resin, and the like can be given. Among them, an epoxy (meth) acrylate resin and an acrylic resin are preferable. These can be used individually by 1 type or in mixture of multiple types.
<アルカリ可溶性樹脂(c1)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、多塩基酸及び/又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
<アルカリ可溶性樹脂(c2)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、及び多塩基酸及び/又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 The alkali-soluble resin used in the present invention is particularly excellent in the following alkali-soluble resin (c1) and / or alkali-soluble resin (c2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth) acrylate resin”). It is preferably used from the viewpoint of plate making.
<Alkali-soluble resin (c1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.
これらの内、感度の点から、特に好ましいものは(メタ)アクリル酸である。 Examples of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as α-position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- ( (Meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) Acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) acryloyl Loxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ-butyrolactone, Monomers added with lactones such as δ-valerolactone, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate with (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) Monomer with added acid (anhydride) such as maleic acid, (meth) acrylic acid dimer And the like.
Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
α,β-不飽和モノカルボン酸又は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、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、引き続く多塩基酸及び/又はその無水物との反応も不十分となる。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が未反応物として残存する。いずれの場合も硬化特性が悪化する傾向が認められる。 The epoxy resin, α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents. When the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated groups introduced is insufficient, and the subsequent polybasic acid and / or anhydride thereof The reaction with is also 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 α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.
カルボキシル基含有エポキシ(メタ)アクリレート樹脂は、通常、エポキシ樹脂とα,β-不飽和モノカルボン酸又は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の反応物に、多塩基酸及び/又はその無水物を混合した後、もしくは、エポキシ樹脂とα,β-不飽和モノカルボン酸又は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の反応物に、多塩基酸及び/又はその無水物及び多官能アルコールを混合した後に、加温することにより得られる。この場合、多塩基酸及び/又はその無水物と多官能アルコールの混合順序に、特に制限はない。加温により、エポキシ樹脂とα,β-不飽和モノカルボン酸又は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の反応物と多官能アルコールとの混合物中に存在するいずれかの水酸基に対して多塩基酸及び/又はその無水物が付加反応する。 In addition, it is good also as what introduce | transduced polyfunctional alcohol, such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of addition reaction of this polybasic acid and / or its anhydride.
The carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited. Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating. To the polybasic acid and / or its anhydride.
また、本発明で用いる(C)アルカリ可溶性樹脂は、前述のカルボキシル基含有エポキシ(メタ)アクリレート樹脂の一部を、本発明の性能を損なわない限り、他のバインダー樹脂に置き換えてもよい。即ち、カルボキシル基含有エポキシ(メタ)アクリレート樹脂と他のバインダー樹脂を併用してもよい。この場合において、アルカリ可溶性樹脂(C)アルカリ可溶性樹脂におけるカルボキシル基含有エポキシ(メタ)アクリレート樹脂の割合を、50質量%以上、特に80質量%以上とすることが好ましい。 The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or as a mixture of two or more resins.
Moreover, (C) alkali-soluble resin used by this invention may replace a part of above-mentioned carboxyl group-containing epoxy (meth) acrylate resin with another binder resin, unless the performance of this invention is impaired. That is, a carboxyl group-containing epoxy (meth) acrylate resin and another binder resin may be used in combination. In this case, the proportion of the carboxyl group-containing epoxy (meth) acrylate resin in the alkali-soluble resin (C) alkali-soluble resin is preferably 50% by mass or more, particularly preferably 80% by mass or more.
(D)光重合開始剤は、光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて重合促進剤(連鎖移動剤)、増感色素等の付加剤を添加して使用してもよい。
光重合開始剤としては、例えば、日本国特開昭59-152396号公報、日本国特開昭61-151197号各公報に記載のチタノセン化合物を含むメタロセン化合物;日本国特開2000-56118号公報に記載のヘキサアリールビイミダゾール誘導体;日本国特開平10-39503号公報記載のハロメチル化オキサジアゾール誘導体、ハロメチル-s-トリアジン誘導体、N-フェニルグリシン等のN-アリール-α-アミノ酸類、N-アリール-α-アミノ酸塩類、N-アリール-α-アミノ酸エステル類等のラジカル活性剤、α-アミノアルキルフェノン誘導体;日本国特開2000-80068号公報、日本国特開2006-36750号公報等に記載されているオキシムエステル誘導体等が挙げられる。 <(D) Photopolymerization initiator>
(D) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.
Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and JP-A No. 2000-56118. N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503; Radical activators such as -aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750 And the oxime ester derivatives described in the above.
オキシム系化合物としては、下記一般式(3)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(3a)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 and plate-making properties, and in the case of using an alkali-soluble resin containing a phenolic hydroxyl group, in terms of sensitivity. In particular, such oxime derivatives (oxime ester and ketoxime ester compounds) excellent in sensitivity are useful.
Examples of the oxime compound include a compound containing a structural moiety represented by the following general formula (3), and preferably include an oxime ester compound represented by the following general formula (3a).
なお、R21aはR21b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。)。 In the formula (3a), R 21a represents a hydrogen atom 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, C2-C10 alkoxycarbonyl group, C7-C20 aryloxycarbonyl group, or C1-C1 0 represents a cycloalkylalkyl group. R 21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R 21a may form a ring together with R 21b , and the linking group may be a C 1-10 alkylene group 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).
上記一般式(3a)におけるR21a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(3a)におけるR21b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 22 in the general formula (3) and R 22a in the general formula (3a) 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 21a in the general formula (3a) 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 21b in the general formula (3a) is preferably an optionally substituted carbazoyl group, an optionally substituted thioxanthonyl group, or an optionally substituted phenyl sulfide group.
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。 Moreover, as an arbitrary substituent in the said General formula (3) and (3a), an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an amide group etc. are mentioned. It is done.
Specific examples of the oxime ester-based compound suitable for the present invention include the compounds exemplified below, but the oxime ester-based compound is not limited to these compounds.
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。 An oxime ester initiator having a carbazole group having a nitro group is also effective.
Examples of the ketoxime compound include a compound containing a structural moiety represented by the following general formula (4), and preferably an oxime ester compound represented by the following general formula (5).
R23b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、R23aはR23b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。)。 In the above general formula (5), each R 23a may be a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, or a heteroarylalkyl having 1 to 20 carbon atoms. Group, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or heteroarylthio group An alkyl 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, an aryloyl group having 7 to 20 carbon atoms, Heteroaryloyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, 7 to 2 carbon atoms 0 represents an aryloxycarbonyl group or a cycloalkylalkyl group having 1 to 10 carbon atoms.
R 23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.
R 23a may form a ring together with R 23b , 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).
上記一般式(5)におけるR23a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R23b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 24 in the general formula (4) and R 24a 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 23a 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.
In addition, R 23b in the general formula (5) is preferably an optionally substituted carbazoyl group or an optionally substituted phenyl sulfide group.
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。 Moreover, as an arbitrary substituent in the said General formula (4) and (5), an alkyl group, an aryl group, an alicyclic group, a heterocyclic group, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an amide group etc. are mentioned. It is done.
Specific examples of the ketoxime ester-based compound suitable for the present invention include compounds exemplified below, but the ketoxime ester-based compound is not limited to these compounds.
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。 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. In the present invention, (D) the photopolymerization initiator is preferably an oxime ester initiator and / or a ketoxime ester initiator.
The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
その他に、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等の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等のアントラキノン誘導体類;ベンゾフェノン、ミヒラーズケトン、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等のベンゾフェノン誘導体類;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-ヒドロキシシクロへ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)ケトン等のアセトフェノン誘導体類;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等のチオキサントン誘導体類;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等の安息香酸エステル誘導体類;9-フェニルアクリジン、9-(p-メトキシフェニル)アクリジン等のアクリジン誘導体類;9,10-ジメチルベンズフェナジン等のフェナジン誘導体類;ベンズアンスロン等のアンスロン誘導体類等も挙げられる。 The ratio of the photopolymerization initiator in the photosensitive coloring composition of the present invention is usually 0.4 to 15% by mass, preferably 0.5 to 10% by mass, based on the total solid content. If the ratio of the photopolymerization initiator is too much within this range, the developability tends to be reduced, while if it is too small, the preferred colored cured product shape and step may not be formed.
Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Yl) acridine derivatives acridine like; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.
オキシムエステル誘導体類の中でも、ジフェニルスルフィド骨格を有する光重合開始剤が耐溶剤性の観点から好ましく、例えば下記一般式(5-1)で表されるものを用いることができる。 Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.
Among oxime ester derivatives, a photopolymerization initiator having a diphenyl sulfide skeleton is preferable from the viewpoint of solvent resistance. For example, those represented by the following general formula (5-1) can be used.
R25a及びR25bは、それぞれ独立に、R25c、OR25c、CN、OH、又はハロゲン原子を表し、fは0~5の整数を表し、gは0~4の整数を表す。
R25cは、炭素数1~20のアルキル基、炭素数6~30のアリール基、又は炭素数7~30のアリールアルキル基を表す。R25cで表わされる置換基の水素原子は、更にハロゲン原子で置換されていてもよく、R25cで表される置換基のアルキレン部分は、-O-、-S-、-COO-、-OCO-又は-NR25d-により1~5回中断されていてもよい。R25dは、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、又は炭素数7~30のアリールアルキル基を表す。R25cで表される置換基のアルキル部分は、分岐側鎖があってもよく、シクロペンチル又はシクロヘキシルであってもよい。
R26はOH、COOH又は下記一般式(5-2)で表される基を表し、hは0~5の整数を表す。 Here, R 23a and R 24a have the same meaning as in the general formula (5).
R 25a and R 25b each independently represent R 25c , OR 25c , CN, OH, or a halogen atom, f represents an integer of 0 to 5, and g represents an integer of 0 to 4.
R 25c represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The hydrogen atom of the substituent represented by R 25c may be further substituted with a halogen atom, and the alkylene moiety of the substituent represented by R 25c is —O—, —S—, —COO—, —OCO. It may be interrupted 1 to 5 times by-or -NR 25d- . R 25d represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl part of the substituent represented by R 25c may have a branched side chain, and may be cyclopentyl or cyclohexyl.
R 26 represents OH, COOH or a group represented by the following general formula (5-2), and h represents an integer of 0 to 5.
R26bは、炭素数1~20のアルキレン基、炭素数6~30のアリーレン基、又は炭素数7~30のアリーレンアルキレン基を表す。
R26bで表される置換基のアルキレン部分は、-O-、-S-、-COO-又は-OCO-により1~5回中断されていてもよい。R26bで表される置換基のアルキレン部分は分岐側鎖があってもよく、シクロヘキシレンであってもよい。
R26cは、OH又はCOOHを表し、iは1~3の整数を表す。
*は結合手を示す。 In the formula (5-2), R 26a represents —O—, —S—, —OCO— or —COO—.
R 26b represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 30 carbon atoms, or an arylene alkylene group having 7 to 30 carbon atoms.
The alkylene part of the substituent represented by R 26b may be interrupted 1 to 5 times by —O—, —S—, —COO— or —OCO—. The alkylene part of the substituent represented by R 26b may have a branched side chain or cyclohexylene.
R 26c represents OH or COOH, and i represents an integer of 1 to 3.
* Indicates a bond.
光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、日本国特開平4-221958号、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、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、日本国特開平5-289335号に記載の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、日本国特開昭54-155292号、日本国特公昭45-37377号、日本国特開昭48-84183号、日本国特開昭52-112681号、日本国特開昭58-15503号、日本国特開昭60-88005号、日本国特開昭59-56403号、日本国特開平2-69号、日本国特開昭57-168088号、日本国特開平5-107761号、日本国特開平5-210240号、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。 A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
A sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity. As sensitizing dyes, xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335 are described. A coumarin dye having a heterocyclic ring, a 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, a pyromethene dye described in JP-A-6-19240, Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Special Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112682, Japan JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57 No. 168,088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP Japanese Patent Laid-Open No. 4-288818.
増感色素もまた1種を単独で用いてもよく、2種以上を併用してもよい。 Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (P-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine P-dialkylaminophenyl group-containing compounds such as Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
本発明の感光性着色組成物においては、更に光重合性モノマー(光重合性化合物)を含むことが、感度等の点で好ましい。
本発明に用いられる光重合性モノマーとしては、分子内にエチレン性不飽和基を少なくとも1個有する化合物(以下、「エチレン性単量体」と称することがある)を挙げることができる。具体的には、例えば(メタ)アクリル酸、(メタ)アクリル酸アルキルエステル、アクリロニトリル、スチレン、及びエチレン性不飽和結合を1個有するカルボン酸と、多価又は1価アルコールのモノエステル、等が挙げられる。 <Photopolymerizable monomer>
In the photosensitive coloring composition of this invention, it is preferable from points, such as a sensitivity, that a photopolymerizable monomer (photopolymerizable compound) is further included.
Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.
かかる多官能エチレン性単量体の例としては、例えば脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルなどが挙げられる。 In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.
多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物等が挙げられる。 Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.
上記ウレタン(メタ)アクリレート類としては、例えば、DPHA-40H、UX-5000、UX-5002D-P20、UX-5003D、UX-5005(日本化薬社製)、U-2PPA、U-6LPA、U-10PA、U-33H、UA-53H、UA-32P、UA-1100H(新中村化学工業社製)、UA-306H、UA-510H、UF-8001G(協栄社化学社製)、UV-1700B、UV-7600B、UV-7605B、UV-7630B、UV7640B(日本合成化学社製)等が挙げられる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。 In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical).
These may be used alone or in combination of two or more.
本発明の感光性着色組成物には、上述の成分の他、有機溶剤、シランカップリング剤等の密着向上剤、塗布性向上剤、現像改良剤、紫外線吸収剤、酸化防止剤、界面活性剤、顔料誘導体等を適宜配合することができる。 <Other compounding components of photosensitive coloring composition>
In addition to the above-mentioned components, the photosensitive coloring composition of the present invention includes adhesion improvers such as organic solvents and silane coupling agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, and surfactants. In addition, pigment derivatives and the like can be appropriately blended.
本発明の感光性着色組成物は、通常、(A)色材、(B)分散剤、(C)アルカリ可溶性樹脂、(D)光重合開始剤、及び必要に応じて使用される光重合性モノマー、その他の各種材料が、有機溶剤に溶解又は分散した状態で使用される。
有機溶剤としては、沸点が100~300℃の範囲のものを選択するのが好ましい。より好ましくは120~280℃の沸点をもつ溶剤である。 (1) Organic solvent The photosensitive coloring composition of the present invention is usually used as (A) a color material, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and as required. The photopolymerizable monomer and other various materials used are dissolved or dispersed in an organic solvent.
It is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. A solvent having a boiling point of 120 to 280 ° C. is more preferable.
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、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モノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ-n-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、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ-n-ブチルエーテル、メトキシメチルペンタノール、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モノメチルエーテル、3-メチル-3-メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類;
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類; Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
エチレングリコールジアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサノールジアセテートなどのグリコールジアセテート類;
シクロヘキサノールアセテートなどのアルキルアセテート類;
アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような1価又は多価アルコール類;
n-ペンタン、n-オクタン、ジイソブチレン、n-ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類;
シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類; Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、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、γ-ブチロラクトンのような鎖状又は環状エステル類;
3-メトキシプロピオン酸、3-エトキシプロピオン酸のようなアルコキシカルボン酸類;
ブチルクロリド、アミルクロリドのようなハロゲン化炭化水素類;
メトキシメチルペンタノンのようなエーテルケトン類;
アセトニトリル、ベンゾニトリルのようなニトリル類等。 Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.
これらの有機溶剤は、単独で用いてもよく、2種以上を併用してもよい。 Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("Cerosolve" is a registered trademark, the same shall apply hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name).
These organic solvents may be used alone or in combination of two or more.
また、グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の有機溶剤を併用してもよい。併用する有機溶剤として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、特に組成物中の構成成分の溶解性からプロピレングリコールモノメチルエーテルが好ましい。なお、グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる着色樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、溶剤中のグリコールモノアルキルエーテル類の割合は5質量%~30質量%が好ましく、5質量%~20質量%がより好ましい。 Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.
好ましい高沸点溶剤として、例えば前述の各種溶剤の中ではジエチレングリコールモノ-n-ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサノールジアセテート、トリアセチンなどが挙げられる。 The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is separately contained. It doesn't have to be.
Preferred high boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
本発明の感光性着色組成物には、基板との密着性を改善するため、密着向上剤を含有させてもよい。密着向上剤としては、シランカップリング剤、燐酸基含有化合物等が好ましい。
シランカップリング剤の種類としては、エポキシ系、(メタ)アクリル系、アミノ系等種々のものを1種を単独で、或いは2種以上を混合して使用できる。 (2) Adhesion improver The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
As the kind of the silane coupling agent, various kinds such as epoxy, (meth) acrylic and amino can be used alone or in combination of two or more.
燐酸基含有化合物としては、(メタ)アクリロイル基含有ホスフェート類が好ましく、下記一般式(g1)、(g2)又は(g3)で表されるものが好ましい。 Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Isocyanate silanes such as 3-isocyanatopropyltriethoxysilane are mentioned, and epoxy silane silane coupling agents are particularly preferable.
As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.
これらの燐酸基含有化合物も1種類を単独で用いても、2種以上を組み合わせて使用してもよい。 In the above general formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2 or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
本発明の感光性着色組成物には、塗布性向上ため、界面活性剤を含有させてもよい。 (3) Surfactant The photosensitive coloring composition of the present invention may contain a surfactant in order to improve coatability.
このような界面活性剤としては、例えば、TSF4460(ジーイー東芝シリコーン社製)、DFX-18(ネオス社製)、BYK-300、BYK-325、BYK-330(ビックケミー社製)、KP340(信越シリコーン社製)、F-470、F-475、F-478、F-559(DIC社製)、SH7PA(トーレシリコーン社製)、DS-401(ダイキン社製)、L-77(日本ユニカー社製)、FC4430(住友3M社製)等が挙げられる。
なお、界面活性剤は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。 As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.
Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (DIC), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 (Nihon Unicar) ), FC4430 (manufactured by Sumitomo 3M), and the like.
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
本発明の感光性着色組成物には、分散性、保存性向上のため、分散助剤として顔料誘導体を含有させてもよい。
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、中でもフタロシアニン系、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。 (4) Pigment derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine Among them, derivatives such as phthalocyanines and quinophthalones are preferable.
Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
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、特に感光性着色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。 (5) Photoacid generator The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and has a crosslinking agent such as a melamine compound due to the action of an acid generated upon exposure. The crosslinking reaction will proceed. Among such photoacid generators, those having a high solubility in a solvent, particularly in a solvent used in a photosensitive coloring 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.
本発明の感光性着色組成物には、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(6)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。 (6) Crosslinking agent A crosslinking agent can be further added to the photosensitive coloring composition of the present invention. For example, a melamine or guanamine compound can be used. Examples of these cross-linking agents include melamine or guanamine compounds represented by the following general formula (6).
ここで、炭素数6~12のアリール基は典型的にはフェニル基、1-ナフチル基又は2-ナフチル基であり、これらのフェニル基やナフチル基には、アルキル基、アルコキシ基、ハロゲン原子などの置換基が結合していてもよい。アルキル基及びアルコキシ基は、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基は、上記のなかでも、メチル基又はエチル基、とりわけメチル基であるのが好ましい。 In the formula (6), R 61 represents a —NR 66 R 67 group or an aryl group having 6 to 12 carbon atoms, and when R 61 is a —NR 66 R 67 group, R 62 , R 63 , R 64 , R 65 one of R 66 and R 67, and R 61 represents R 62, R 63, one of R 64 and R 65 are -CH 2 oR 68 group in the case of an aryl group having 6 to 12 carbon atoms, R 62 , R 63 , R 64 , R 65 , R 66 and R 67 , independently of one another, represent hydrogen or a —CH 2 OR 68 group, wherein R 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. To express.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, 1-naphthyl group or 2-naphthyl group, and these phenyl group and naphthyl group include an alkyl group, an alkoxy group, a halogen atom, etc. May be bonded to each other. Each of the alkyl group and the alkoxy group may have about 1 to 6 carbon atoms. Alkyl group represented by R 68 is, among the above, methyl group or an ethyl group, especially a methyl group.
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。 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.
重合促進剤として、また、基板への密着性の向上のため、メルカプト化合物を添加することも可能である。 (7) Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator and to improve adhesion to the substrate.
本発明の感光性着色組成物において、(A)色材の含有量は、感光性着色組成物中の全固形分量に対して通常10質量%以上、20質量%以上であることが好ましく、また、通常50質量%以下である。(A)色材の含有量が少なすぎると、十分な光学濃度(OD)が得られない場合があり、また、逆に(A)色材の含有量が多すぎると、十分な画像形成性が得られなくなることがある。また、(A)色材100質量%に対する(A-1)有機黒色顔料の含有割合は、通常10質量%以上、好ましくは30質量%以上であり、また、通常100質量%以下である。(A)色材中の(A-1)有機黒色顔料の含有割合が少なすぎると、十分な光学濃度(OD)が得られない場合がある。 <Ingredient compounding amount in photosensitive coloring composition>
In the photosensitive coloring composition of the present invention, the content of (A) the coloring material is usually preferably 10% by mass or more and 20% by mass or more with respect to the total solid content in the photosensitive coloring composition. Usually, it is 50 mass% or less. (A) If the content of the color material is too small, sufficient optical density (OD) may not be obtained. Conversely, if the content of (A) the color material is too large, sufficient image forming properties may be obtained. May not be obtained. In addition, the content ratio of the (A-1) organic black pigment to (A) 100% by mass of the color material is usually 10% by mass or more, preferably 30% by mass or more, and usually 100% by mass or less. If the content of the (A-1) organic black pigment in the color material (A) is too small, a sufficient optical density (OD) may not be obtained.
また、本発明の感光性着色組成物中に占める増感色素の配合割合は感度の観点から感光性着色組成物中の全固形分中、通常20質量%以下、好ましくは15質量%以下、更に好ましくは10質量%以下である。 (D) If the blending ratio of the photopolymerization initiator system component composed of a photopolymerization initiator and a polymerization accelerator is extremely low, the sensitivity to exposure light may be reduced. Solubility in the developer may be reduced, leading to poor development.
The blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. Preferably it is 10 mass% or less.
なお、本発明の感光性着色組成物は、前述の有機溶剤を使用して、その固形分濃度が通常5~50質量%、好ましくは10~30質量%となるように調液される。 When a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0, based on the total solid content in the photosensitive coloring composition. 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.
The photosensitive coloring composition of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
本発明の感光性着色組成物は、ブラックマトリクス形成用に好適に使用することができ、係る観点から黒色を呈していることが好ましく、その塗膜の膜厚1μm当たりの光学濃度(OD)が1.0以上であることが好ましい。 <Physical properties of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be suitably used for forming a black matrix, and preferably exhibits a black color from such a viewpoint, and has an optical density (OD) per 1 μm film thickness of the coating film. It is preferable that it is 1.0 or more.
本発明の感光性着色組成物(以下、「レジスト」と称することがある。)は、常法に従って製造される。
通常、(A)色材は、予め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、ホモジナイザー等を用いて分散処理するのが好ましい。分散処理により(A)色材が微粒子化されるため、レジストの塗布特性が向上する。 <Method for producing photosensitive coloring composition>
The photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, it is preferable to disperse (A) the color material in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the colorant (A) is finely divided by the dispersion treatment, the resist coating characteristics are improved.
このように、レジストを製造する工程において、(A)色材、有機溶剤、及び(B)分散剤を少なくとも含有する顔料分散液を製造することが好ましい。顔料分散液に用いることができる(A)色材、有機溶剤、及び(B)分散剤としては、それぞれ感光性着色組成物に用いることができるものとして記載したものを好ましく採用することができる。 The dispersion treatment is usually preferably carried out in a system in which (A) a color material, an organic solvent, (B) a dispersant, and (C) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as dispersion treatment). The mixture to be provided and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”). In particular, it is preferable to use a polymer dispersant as the dispersant (B) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
Thus, in the step of producing a resist, it is preferable to produce a pigment dispersion containing at least (A) a color material, an organic solvent, and (B) a dispersant. As (A) colorant, organic solvent, and (B) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive coloring composition can be preferably employed.
サンドグラインダーで(A)色材を分散させる場合には、0.1~8mm程度の径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常0℃から100℃であり、好ましくは室温から80℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。レジストの20度鏡面光沢度(JIS Z8741)が50~300の範囲となるように、インキの光沢を制御するのが分散の目安である。レジストの光沢度が低い場合には、分散処理が十分でなく荒い顔料(色材)粒子が残っていることが多く、現像性、密着性、解像性等が不十分となる可能性がある。また、光沢値が上記範囲を超えるまで分散処理を行うと、顔料が破砕して超微粒子が多数生じるため、却って分散安定性が損なわれる傾向がある。 In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the colored resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the color material (A) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
次に、上記分散処理により得られたインキと、レジスト中に含まれる、上記の他の成分を混合し、均一な溶液とする。レジスト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、得られたレジストはフィルター等により濾過処理するのが望ましい。 The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered by a filter or the like.
本発明の感光性着色組成物を硬化させることで、硬化物を得ることができる。感光性着色組成物を硬化してなる硬化物は、ブラックマトリクスや着色スペーサーとして好適に用いることができる。 [Cured product]
A cured product can be obtained by curing the photosensitive coloring composition of the present invention. A cured product obtained by curing the photosensitive coloring composition can be suitably used as a black matrix or a colored spacer.
次に、本発明の感光性着色組成物を用いたブラックマトリクスについて、その製造方法に従って説明する。 [Black matrix]
Next, the black matrix using the photosensitive coloring composition of the present invention will be described in accordance with its production method.
ブラックマトリクスを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。おもに透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ(メタ)アクリル系樹脂などの熱硬化性樹脂シート、又は各種ガラスなどが挙げられる。この中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にITO、IZO等の透明電極が成膜されている場合もある。透明基板以外では、TFTアレイ上に形成することも可能である。 (1) Support The support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, but the material is, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, a sheet made of a thermoplastic resin such as polycarbonate, polymethyl methacrylate or polysulfone, or an epoxy resin. And thermosetting resin sheets such as unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. Other than the transparent substrate, it can be formed on the TFT array.
透明基板の厚さは、通常0.05~10mm、好ましくは0.1~7mmの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常0.01~10μm、好ましくは0.05~5μmの範囲である。 The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, in order to improve surface properties such as adhesiveness. .
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. When a thin film forming process of various resins is performed, the film thickness is usually 0.01 to 10 μm, preferably 0.05 to 5 μm.
上述の本発明の感光性着色組成物により、本発明のブラックマトリクスを形成するには、透明基板上に本発明の感光性着色組成物を塗布して乾燥した後、該感光性着色組成物の上にフォトマスクを置き、該フォトマスクを介して画像露光、現像、必要に応じて熱硬化或いは光硬化することによりブラックマトリクスを形成させる。
尚、本発明のブラックマトリクスはTFT素子基板上に形成させるのに有効であるが、その構成はCOA、BOAそれぞれの方式において特に限定されるものではなく、種々の構成への対応が可能である。 (2) Black matrix In order to form the black matrix of the present invention with the above-described photosensitive coloring composition of the present invention, the photosensitive coloring composition of the present invention is applied on a transparent substrate and dried, and then the photosensitive matrix is coated. A black mask is formed by placing a photomask on the coloring composition and exposing the image through the photomask, developing, and thermosetting or photocuring as necessary.
The black matrix of the present invention is effective for forming on the TFT element substrate, but the configuration is not particularly limited in each of the COA and BOA systems, and can be applied to various configurations. .
(3-1)感光性着色組成物の塗布
ブラックマトリクス用の感光性着色組成物の透明基板上への塗布は、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、又は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く、異物発生が抑制されるなど、総合的な観点から好ましい。 (3) Formation of black matrix (3-1) Application of photosensitive coloring composition The photosensitive coloring composition for black matrix is applied on a transparent substrate by spinner method, wire bar method, flow coating method, die coating method. , Roll coating method or spray coating method. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.
基板に感光性着色組成物を塗布した後の塗膜の乾燥は、ホットプレート、IRオーブン、又はコンベクションオーブンを使用した乾燥法により行うのが好ましい。乾燥の条件は、前記溶剤成分の種類、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、40~200℃の温度で15秒~5分間の範囲で選ばれ、好ましくは50~130℃の温度で30秒~3分間の範囲で選ばれる。
乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上するが、高すぎると(C)アルカリ可溶性樹脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、この塗膜の乾燥工程は、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法であってもよい。 (3-2) Drying of coating film The coating film after the photosensitive coloring composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected within the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, if the drying temperature is too high, (C) the alkali-soluble resin may be decomposed to induce thermal polymerization and cause poor development. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
画像露光は、感光性着色組成物の塗膜上に、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。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、光重合性の塗膜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てもよい。上記の画像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、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。 (3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically 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 an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
本発明に係るブラックマトリクスは、感光性着色組成物による塗膜を、上記の光源によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性化合物とを含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。この水溶液には、更に有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。 (3-4) Development The black matrix according to the present invention comprises an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after the coating film made of the photosensitive coloring composition is subjected to image exposure with the above light source. An image can be formed on a substrate by development using a film. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
現像の後の基板には、熱硬化処理又は光硬化処理、好ましくは熱硬化処理を施す。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5~60分間の範囲で選ばれる。
以上のようにして形成させたブラックマトリクスの線幅は通常3~50μm、好ましくは4~30μm、高さは通常0.5~5μm、好ましくは1~4μmである。また、体積抵抗率は1×1013Ω・cm以上、好ましくは1×1014Ω・cm以上であり、比誘電率は6以下、好ましくは5以下であり、通常2以上である。
さらに、厚さ1μm当たりの光学濃度(OD)が1.2以上、好ましくは1.5以上、より好ましくは1.8以上であり、通常4.0以下である。ここで、光学濃度(OD)は後述する方法にて測定した値である。 (3-5) Thermosetting treatment The substrate after development is subjected to thermosetting treatment or photocuring treatment, preferably thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is in the range of 5 to 60 minutes.
The line width of the black matrix formed as described above is usually 3 to 50 μm, preferably 4 to 30 μm, and the height is usually 0.5 to 5 μm, preferably 1 to 4 μm. The volume resistivity is 1 × 10 13 Ω · cm or more, preferably 1 × 10 14 Ω · cm or more, and the relative dielectric constant is 6 or less, preferably 5 or less, and usually 2 or more.
Furthermore, the optical density (OD) per 1 μm thickness is 1.2 or more, preferably 1.5 or more, more preferably 1.8 or more, and usually 4.0 or less. Here, the optical density (OD) is a value measured by a method described later.
本実施の形態の感光性着色組成物は、ブラックマトリクス以外に着色スペーサー用のレジストとして使用することも可能である。スペーサーを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り、着色スペーサーはこれを防止するために用いられ、例えば、日本国特開平8-234212号公報にスペーサーを遮光性とすることが記載されている。着色スペーサーは着色スペーサー用のマスクを用いる以外は前述のブラックマトリクスと同様の方法で形成することができる。 [Coloring spacer]
The photosensitive coloring composition of this Embodiment can also be used as a resist for coloring spacers other than a black matrix. When a spacer is used in a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this, for example, Japanese Patent Application Laid-Open No. 8-234212. The publication discloses that the spacer is light-shielding. The colored spacer can be formed in the same manner as the black matrix described above except that a mask for the colored spacer is used.
本発明の画像表示装置としては、画像や映像を表示する装置であれば特に限定は受けないが、後述する液晶表示装置や有機EL(Electro Luminesence)ディスプレイ等が挙げられる。 [Image display device]
The image display device of the present invention is not particularly limited as long as it is a device that displays an image or video, and examples thereof include a liquid crystal display device and an organic EL (Electro Luminesence) display described later.
本発明の液晶表示装置は、上述の本発明のブラックマトリクスを用いて作製されたものであり、カラー画素やブラックマトリクスの形成順序や形成位置等特に制限を受けるものではない。
例えば、TFT素子基板上に、本発明のブラックマトリクスを設け、赤色、緑色、青色の画素を形成し、必要に応じてオーバーコート層を形成した後に、更にその上に、画像上にITO、IZO等の透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用される。また一部、平面配向型駆動方式(IPSモード)などの用途においては、透明電極を形成しないこともある。 [Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described black matrix of the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
For example, the black matrix of the present invention is provided on a TFT element substrate, red, green and blue pixels are formed, an overcoat layer is formed as necessary, and further, ITO and IZO are formed on the image. Are used as part of components such as a color display and a liquid crystal display device. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
スペーサーとしては、対向基板とのギャップ(隙間)に応じた大きさのものが用いられ、通常2~8μmのものが好適である。カラーフィルター基板上に、フォトリソグラフィー法によって透明樹脂膜のフォトスペーサー(PS)を形成し、これをスペーサーの代わりに活用することもできる。 As long as the black matrix of the present invention is used, there is no particular limitation on the formation order and formation position of the color pixels and the black matrix.
As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバー内で減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバー内をリークすることによって、液晶を液晶セル内に注入する。液晶セル内の減圧度は、通常、1×10-2~1×10-7Paであるが、好ましくは1×10-3~1×10-6Paである。また、減圧時に液晶セルを加温するのが好ましく、加温温度は通常30~100℃であり、より好ましくは50~90℃である。減圧時の加温保持は、通常10~60分間の範囲とされ、その後液晶中に浸漬される。液晶を注入した液晶セルは、液晶注入口を硬化させたUV硬化樹脂で封止することによって、液晶表示装置(パネル)が完成する。 The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of decompression in the liquid crystal cell is usually 1 × 10 −2 to 1 × 10 −7 Pa, preferably 1 × 10 −3 to 1 × 10 −6 Pa. Further, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is usually 30 to 100 ° C., more preferably 50 to 90 ° C. The warming holding at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is sealed with a UV curable resin in which the liquid crystal injection port is cured, thereby completing a liquid crystal display device (panel).
本発明のブラックマトリクスを用いて本発明の有機ELディスプレイを作製することができる。
本発明のブラックマトリクスを用いて有機ELディスプレイを作製する場合、例えば図1に示すように、まず透明支持基板10上に、着色樹脂組成物により形成されたパターン(すなわち、画素20、及び隣接する画素20の間に設けられたブラックマトリクス(図示せず))が形成されてなるカラーフィルターを作製し、該カラーフィルター上に有機保護層30及び無機酸化膜40を介して有機発光体500を積層することによって、有機EL素子100を作製することができる。なお、画素20及びブラックマトリクスの内、少なくとも一つは本発明の感光性着色組成物を用いて作製されたものである。有機発光体500の積層方法としては、カラーフィルター上面へ透明陽極50、正孔注入層51、正孔輸送層52、発光層53、電子注入層54、及び陰極55を逐次形成していく方法や、別基板上へ形成した有機発光体500を無機酸化膜40上に貼り合わせる方法などが挙げられる。このようにして作製された有機EL素子100を用い、例えば「有機ELディスプレイ」(オーム社,2004年8月20日発光,時任静士、安達千波矢、村田英幸著)に記載された方法等にて、有機ELディスプレイを作製することができる。
なお、本発明のブラックマトリクスは、パッシブ駆動方式の有機ELディスプレイにもアクティブ駆動方式の有機ELディスプレイにも適用可能である。 [Organic EL display]
The organic EL display of the present invention can be produced using the black matrix of the present invention.
When producing an organic EL display using the black matrix of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the
Note that the black matrix of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.
以下の実施例及び比較例で用いた感光性着色組成物の構成成分は次の通りである。
<(A-1)有機黒色顔料>
BASF社製、Irgaphor(登録商標) Black S 0100 CF(下記式(2)で表される化学構造を有する) Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
The components of the photosensitive coloring composition used in the following examples and comparative examples are as follows.
<(A-1) Organic black pigment>
Made by BASF, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (2))
BASF社製、Lumogen(登録商標) Black FK4281
<有機黒色顔料:アニリンブラック>
BASF社製、Paliotol(登録商標) Black L0080 <Organic black pigment: Perylene black>
Lumogen (registered trademark) Black FK4281 manufactured by BASF
<Organic black pigment: aniline black>
PALIOTOL (registered trademark) Black L0080, manufactured by BASF
プロピレングリコールモノメチルエーテルアセテート145質量部を窒素置換しながら攪拌し、120℃に昇温した。ここにスチレン10質量部、グリシジルメタクリレート85.2質量部およびトリシクロデカン骨格を有するモノアクリレート(日立化成社製FA-513M)66質量部を滴下し、および2,2’-アゾビス-2-メチルブチロニトリル8.47質量部を3時間かけて滴下し、更に90℃で2時間攪拌し続けた。次に反応容器内を空気置換に変え、アクリル酸43.2質量部にトリスジメチルアミノメチルフェノール0.7質量部およびハイドロキノン0.12質量部を投入し、100℃で12時間反応を続けた。その後、テトラヒドロ無水フタル酸(THPA)56.2質量部、トリエチルアミン0.7質量部を加え、100℃3.5時間反応させた。こうして得られたアルカリ可溶性樹脂-IのGPCにより測定した重量平均分子量Mwは約8400、酸価は80mgKOH/gであった。 <Alkali-soluble resin-I>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and 2,2′-azobis-2-methyl was added. 8.47 parts by mass of butyronitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I thus obtained was about 8400, and the acid value was 80 mgKOH / g.
日本化薬(株)製「ZCR-1664H」(重量平均分子量Mw=5000~6000、酸価=約60mg-KOH/g)
<アルカリ可溶性樹脂-III> <Alkali-soluble resin-II>
“ZCR-1664H” manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 5000 to 6000, acid value = about 60 mg-KOH / g)
<Alkali-soluble resin-III>
樹脂溶液が透明になったところで、メトキシブチルアセテートで希釈し、固形分50質量%となるよう調製し、酸価131mgKOH/g、GPCで測定したポリスチレン換算の重量平均分子量(Mw)4000のカルボキシル基含有エポキシアクリレート樹脂(c1)を得た。 25 parts by mass of the above-mentioned epoxy acrylate solution, 0.8 parts by mass of trimethylolpropane (TMP), 4.1 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), 2.8 parts by mass of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, the resin solution is diluted with methoxybutyl acetate and prepared to have a solid content of 50% by mass. The carboxyl group has an acid value of 131 mgKOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 4000 measured by GPC. A contained epoxy acrylate resin (c1) was obtained.
日本化薬(株)製「ZCR-1642H」(MW=6500、酸価=98mg-KOH/g) <Alkali-soluble resin-IV>
“ZCR-1642H” manufactured by Nippon Kayaku Co., Ltd. (MW = 6500, acid value = 98 mg-KOH / g)
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3級アミノ基を有する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。アミン価は70mgKOH/g。酸価は1mgKOH/g以下。)
分散剤-Iの全繰り返し単位に占める下記式(1a)、(2a)、及び(3a)の繰り返し単位の含有割合はそれぞれ11.1モル%、22.2モル%、6.7モル%である。 <Dispersant-I>
“DISPERBYK-LPN21116” manufactured by BYK Chemie Co., Ltd. (Acrylic AB block consisting of an A block having a quaternary ammonium base and tertiary amino group in the side chain and a B block having no quaternary ammonium base and amino group) Polymer.Amine value is 70 mgKOH / g. Acid value is 1 mgKOH / g or less.)
The content of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.
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-III>
EFKA社製「EFKA-4300」(側鎖に3級アミノ基とブチル基を有する、アクリル系高分子分散剤。側鎖に4級アンモニウム塩基を有さない。) <Dispersant-II>
"DISPERBYK-2000" manufactured by Big Chemie (acrylic AB block copolymer consisting of an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base)
<Dispersant-III>
“EFKA-4300” manufactured by EFKA (acrylic polymer dispersant having a tertiary amino group and a butyl group in the side chain. No quaternary ammonium base in the side chain)
ルーブリゾール社製「Solsperse12000」
<溶剤-I>
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-II>
MB:3-メトキシブタノール
<光重合開始剤-I> <Pigment derivative>
Lubrizol “Solsperse 12000”
<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxybutanol <Photoinitiator-I>
有機層を飽和炭酸水素ナトリウム水溶液、飽和塩化ナトリウム水溶液で順に洗浄し、無水硫酸マグネシウムを加えて乾燥した。無水硫酸マグネシウムをろ過した後、エバポレーターにより溶媒を留去し、化合物3(1.72g、粗収率78%)を得た。これを精製せずに、次の反応に用いた。 Under a nitrogen atmosphere, Compound 2 (2.13 g, 5 mmol), methanol (22 mL) and concentrated sulfuric acid (5 mg) were placed in a 50 mL three-necked flask, and the mixture was heated to reflux for 3 hours. After cooling, the solvent was concentrated and water (10 mL) and ethyl acetate (30 mL) were added.
The organic layer was washed sequentially with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. After filtering anhydrous magnesium sulfate, the solvent was distilled off by an evaporator to obtain Compound 3 (1.72 g, crude yield 78%). This was used in the next reaction without purification.
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
<光重合性モノマーII>
DPHA-40H:日本化薬(株)製 ウレタンアクリレート
<添加剤-I>
日本化薬(株)製、KAYAMER PM-21(メタクリロイル基含有ホスフェート)
<界面活性剤-I>
DIC(株)製 メガファック F-559 <Photopolymerizable monomer-I>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate <Photopolymerizable monomer II>
DPHA-40H: Nippon Kayaku Co., Ltd. urethane acrylate <Additive-I>
KAYAMER PM-21 (phosphate containing methacryloyl group), manufactured by Nippon Kayaku Co., Ltd.
<Surfactant-I>
DIC Corporation Mega Fuck F-559
表1に記載の顔料、分散剤、分散助剤、アルカリ可溶性樹脂、及び溶剤を、表1に記載の質量比となるように混合した。この溶液をペイントシェーカーにより25~45℃の範囲で3時間分散処理を行った。ビーズとしては、0.5mmφのジルコニアビーズを用い、分散液の2.5倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、顔料分散液-1~7を調製した。 <Preparation of
The pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was obtained. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the completion of dispersion, the beads and dispersion were separated by a filter to prepare
カーボンブラックは、通常のオイルファーネス法で製造した。但し、原料油としては、Na、Ca、S分量の少ないエチレンボトム油を用い、燃焼用にはコークス炉ガスを用いた。更に、反応停止水としては、イオン交換樹脂で処理した純水を用いた。得られたカーボンブラック540gを純水14500gと共にホモミキサーを用い5,000~6,000rpmで30分撹拌しスラリーを得た。このスラリーをスクリュー型撹拌機付容器に移し約1,000rpmで混合しながらエポキシ樹脂「エピコート828」(三菱化学(株)製)60gを溶解したトルエン600gを少量ずつ添加していった。約15分で、水に分散していたカーボンブラックは全量トルエン側に移行し、約1mmの粒となった。 <Coated carbon black dispersion>
Carbon black was produced by a normal oil furnace method. However, as the raw material oil, an ethylene bottom oil having a small amount of Na, Ca, and S was used, and a coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Mitsubishi Chemical Corporation) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
得られた被覆カーボンブラック90質量部に対し、分散剤としてDISPERBYK-167(ビックケミー社製)を20質量部、顔料誘導体としてSolsperse12000(ルーブリゾール社製)を4.5質量部加え、固形分濃度が25質量%となるように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)を加えた。 Next, after draining with a 60 mesh wire net, it was put into a vacuum dryer and dried at 70 ° C. for 7 hours to completely remove toluene and water.
To 90 parts by mass of the resulting coated carbon black, 20 parts by mass of DISPERBYK-167 (manufactured by Big Chemie) as a dispersant and 4.5 parts by mass of Solsperse 12000 (manufactured by Lubrizol) as a pigment derivative are added, and the solid content concentration is increased. Propylene glycol monomethyl ether acetate (PGMEA) was added so that it might become 25 mass%.
上記調製した顔料分散液、被覆カーボンブラック分散液を用いて、固形分中の比率が表2の配合割合となるように各成分を加え、さらに固形分が17質量%となるようにPGMEAを加え、攪拌、溶解させて、感光性着色組成物を調製した。実施例1~8及び比較例1、2及び4は固形分中の顔料濃度を40質量%とし、比較例3は固形分中の顔料濃度を30質量%とした。また、全ての感光性着色組成物において、光重合性モノマーに対するアルカリ可溶性樹脂(分散液中の樹脂も含む)の質量比率を3とし、光重合開始剤を固形分中4質量%、添加剤を0.5質量%、界面活性剤を0.1質量%とした。得られた感光性着色組成物を用いて、後述する方法で評価を行った。 [Examples 1 to 8 and Comparative Examples 1 to 4]
Using the pigment dispersion and the coated carbon black dispersion prepared above, each component was added so that the ratio in the solid content was the mixing ratio shown in Table 2, and further PGMEA was added so that the solid content was 17% by mass. The mixture was stirred and dissolved to prepare a photosensitive coloring composition. In Examples 1 to 8 and Comparative Examples 1, 2 and 4, the pigment concentration in the solid content was 40% by mass, and in Comparative Example 3, the pigment concentration in the solid content was 30% by mass. Moreover, in all the photosensitive coloring compositions, the mass ratio of the alkali-soluble resin (including the resin in the dispersion) to the photopolymerizable monomer is 3, the photopolymerization initiator is 4% by mass in the solid content, and the additive is 0.5% by mass and 0.1% by mass of the surfactant were used. Using the obtained photosensitive coloring composition, it evaluated by the method mentioned later.
調製した感光性着色組成物を最終的な膜厚が2μmとなるようにスピンコーターにてガラス基板に塗布し、1分間減圧乾燥した後に、ホットプレートで100℃にて90秒間乾燥した。230℃で30分間加熱する事で、レジスト塗工基板(基板-1)を得た。得られた基板の光学濃度(OD)を透過濃度計グレタグマクベスD200-IIによって測定し、膜厚を(株)菱化システム製非接触表面・層断面形状計測システム VertScan(R)2.0により測定した。膜厚1μm当たりの光学濃度(OD)を表3に示す。 [Measurement of optical density (OD) per 1 μm]
The prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the final film thickness was 2 μm, dried under reduced pressure for 1 minute, and then dried at 100 ° C. for 90 seconds with a hot plate. A resist-coated substrate (substrate-1) was obtained by heating at 230 ° C. for 30 minutes. The optical density (OD) of the obtained substrate was measured with a transmission densitometer Gretag Macbeth D200-II, and the film thickness was measured with a non-contact surface / layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd. It was measured. Table 3 shows the optical density (OD) per 1 μm of film thickness.
基板-1の作製方法において、ガラス基板の代わりにクロム蒸着膜を有するガラス基板を用いる以外は同様にして基板(基板-2)を作製した。このサンプルのクロム膜を主電極として、レジスト塗膜上に金の対向電極を蒸着法により形成した。また、HP(現Agilent)社製「LCRメーター4284A」を用いて、1kHz・1Vにおける比誘電率を測定した。結果を表3に示す。 [Measurement of relative permittivity]
A substrate (substrate-2) was prepared in the same manner as in the method for preparing substrate-1, except that a glass substrate having a chromium vapor deposition film was used instead of the glass substrate. Using the chromium film of this sample as a main electrode, a gold counter electrode was formed on the resist coating film by vapor deposition. Moreover, the relative dielectric constant at 1 kHz · 1 V was measured using “LCR meter 4284A” manufactured by HP (current Agilent). The results are shown in Table 3.
基板-1と同様の方法でホットプレートによる乾燥を行った。このサンプルを開口20μmの直線パターンのあるネガタイプのマスクを通して高圧水銀灯で像露光した(照度30mW/cm2、露光量20mJ/cm2)。この時、サンプルとマスクとの距離は200μmとした。その後、温度25℃で、KOH濃度0.05質量%の現像液を用いてスプレー現像した。現像時間は未露光部の溶解時間の1.5倍とした。得られた線状パターンの線幅の結果を表3に示す。ただし、比較例1及び2のレジストを用いた場合、10分間現像してもパターンが得られなかった。 [Plate making characteristics]
Drying with a hot plate was performed in the same manner as for substrate-1. This sample was image-exposed with a high-pressure mercury lamp through a negative type mask having a linear pattern with an opening of 20 μm (
<顔料分散液-8~11の調製>
表4に記載の顔料、分散剤、分散助剤、アルカリ可溶性樹脂、及び溶剤を、表4に記載の質量比となるように混合した。この溶液をペイントシェーカーにより25~45℃の範囲で3時間分散処理を行った。ビーズとしては、0.5mmφのジルコニアビーズを用い、分散液の2.5倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、顔料分散液-8~11を調製した。 [Dispersibility evaluation]
<Preparation of pigment dispersions-8 to 11>
The pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 4 were mixed so that the mass ratio described in Table 4 was obtained. This solution was subjected to a dispersion treatment in the range of 25 to 45 ° C. for 3 hours using a paint shaker. As the beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare pigment dispersions-8 to 11.
上記調製した顔料分散液を用いて、固形分中の比率が表5の配合割合となるように各成分を加え、さらに固形分が17質量%となるようにPGMEAを加え、攪拌、溶解させて、感光性着色組成物を調製した。
また、得られた各感光性着色組成物について東機産業株式会社製 RC80L型粘度計(測定条件:23℃、50rpm)によりその粘度を測定した。結果を表5に示す。 [Example 9 and Comparative Examples 5 to 7]
Using the pigment dispersion prepared above, add each component so that the ratio in the solid content is the blending ratio in Table 5, and add PGMEA so that the solid content is 17% by mass, and stir and dissolve. A photosensitive coloring composition was prepared.
Moreover, the viscosity was measured about each obtained photosensitive coloring composition by the Toki Sangyo Co., Ltd. RC80L type | mold viscosity meter (measuring conditions: 23 degreeC, 50 rpm). The results are shown in Table 5.
20 画素
30 有機保護層
40 無機酸化膜
50 透明陽極
51 正孔注入層
52 正孔輸送層
53 発光層
54 電子注入層
55 陰極
100 有機EL素子
500 有機発光体 DESCRIPTION OF
Claims (17)
- (A)色材、(B)分散剤、(C)アルカリ可溶性樹脂、及び(D)光重合開始剤を少なくとも含有する感光性着色組成物であって、
前記(A)色材が(A-1)下記一般式(1)で表される化合物、その幾何異性体、その塩、またはその幾何異性体の塩である有機黒色顔料を含み、かつ、
前記(B)分散剤が4級アンモニウム塩基を官能基として有する高分子分散剤を含む感光性着色組成物。
[式(1)中、R1およびR6は互いに独立して水素原子、CH3、CF3、フッ素原子または塩素原子である;R2、R3、R4、R5、R7、R8、R9およびR10は他の全てから互いに独立して水素原子、ハロゲン原子、R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N=CH2、N=CHR11、N=CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11またはSO2NR11R12である;且つ、R2とR3、R3とR4、R4とR5、R7とR8、R8とR9、及びR9とR10からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、または酸素原子、硫黄原子、NH若しくはNR11ブリッジによって互いに結合することもできる;R11およびR12は互いに独立して、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基または炭素数2~12のアルキニル基である。] A photosensitive coloring composition containing at least (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
The colorant (A) comprises (A-1) an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer;
The photosensitive coloring composition in which the said (B) dispersing agent contains the polymeric dispersing agent which has a quaternary ammonium base as a functional group.
[In the formula (1), R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom; R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9, and R 10 are independently of each other hydrogen atoms, halogen atoms, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11. , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N = CH 2 , N = CHR 11 , N = CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , S O 2 NHR 11 or SO 2 NR 11 R 12 ; and R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and R 9 At least one combination selected from the group consisting of R 10 may be directly bonded to each other, or may be bonded to each other by an oxygen atom, sulfur atom, NH or NR 11 bridge; R 11 and R 12 are independently of each other; An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ] - 前記一般式(1)において、
式中、R2、R4、R5、R7、R9およびR10は互いに独立して水素原子、フッ素原子または塩素原子であり、R3およびR8は互いに独立して水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3HまたはSO3 -であり、R1はR6と同一であり、R2はR7と同一であり、R3はR8と同一であり、R4はR9と同一であり、R5はR10と同一である、請求項1に記載の感光性着色組成物。 In the general formula (1),
In the formula, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom, and R 3 and R 8 are each independently a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N (CH 3 ) 2 , N (CH 3 ) (C 2 H 5 ), N (C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , R 1 is the same as R 6 , R 2 is the same as R 7 , R 3 is the same as R 8 , The photosensitive coloring composition according to claim 1, wherein R 4 is the same as R 9 and R 5 is the same as R 10 . - 前記高分子分散剤が、さらに3級アミンを官能基として有する、請求項1又は請求項2に記載の感光性着色組成物。 The photosensitive coloring composition according to claim 1 or 2, wherein the polymer dispersant further has a tertiary amine as a functional group.
- 前記(C)アルカリ可溶性樹脂が、下記アルカリ可溶性樹脂(c1)及び下記アルカリ可溶性樹脂(c2)の少なくともいずれかを含む、請求項1~請求項3のいずれか1項に記載の感光性着色組成物。
<アルカリ可溶性樹脂(c1)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、多塩基酸及び/又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
<アルカリ可溶性樹脂(c2)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又は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、並びに多塩基酸及び/又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。 The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (C) alkali-soluble resin contains at least one of the following alkali-soluble resin (c1) and the following alkali-soluble resin (c2). object.
<Alkali-soluble resin (c1)>
It was obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
<Alkali-soluble resin (c2)>
An α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this. - 前記(A)色材が、さらに(A-2)有機着色顔料を含有する、請求項1~請求項4のいずれか1項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 4, wherein the (A) coloring material further contains (A-2) an organic coloring pigment.
- 前記(A-2)有機着色顔料が、以下の顔料のうち少なくとも1種以上を含有する、請求項5に記載の感光性着色組成物。
青:カラーインデックスピグメントブルー60、又は15:6
赤:カラーインデックスピグメントレッド177、254、又は272
紫:カラーインデックスピグメントバイオレット23、又は29
橙:カラーインデックスピグメントオレンジ43、64、又は72 The photosensitive coloring composition according to claim 5, wherein the (A-2) organic coloring pigment contains at least one of the following pigments.
Blue: Color index pigment blue 60 or 15: 6
Red: Color index pigment red 177, 254, or 272
Purple: Color Index Pigment Violet 23 or 29
Orange: Color index pigment orange 43, 64, or 72 - 前記(A)色材100質量%に対する、前記(A-1)有機黒色顔料の含有割合が30~90質量%、(A-2)有機着色顔料の含有割合が10~70質量%である、請求項5または請求項6に記載の感光性着色組成物。 The content ratio of the (A-1) organic black pigment is 30 to 90 mass% and the content ratio of the (A-2) organic color pigment is 10 to 70 mass% with respect to 100 mass% of the (A) color material. The photosensitive coloring composition of Claim 5 or Claim 6.
- 前記(A)色材がさらに(A-3)カーボンブラックを含有する、請求項1~請求項7のいずれか1項に記載の感光性着色組成物。 The photosensitive coloring composition according to any one of claims 1 to 7, wherein the (A) coloring material further contains (A-3) carbon black.
- 前記(A)色材100質量%に対する、前記(A-1)有機黒色顔料の含有割合が50~90質量%、(A-3)カーボンブラックの含有割合が10~50質量%である、請求項8に記載の感光性着色組成物。 The content ratio of the (A-1) organic black pigment is 50 to 90% by mass and the content ratio of (A-3) carbon black is 10 to 50% by mass with respect to 100% by mass of the (A) color material. Item 9. The photosensitive coloring composition according to Item 8.
- 前記(D)光重合開始剤が、オキシムエステル開始剤、及び/又はケトオキシムエステル開始剤である、請求項1~請求項9のいずれか1項に記載の感光性着色組成物。 10. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (D) is an oxime ester initiator and / or a ketoxime ester initiator.
- 請求項1~請求項10のいずれか1項に記載の感光性着色組成物を硬化して得られる硬化物。 A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 10.
- 請求項11に記載の硬化物から形成されるブラックマトリクス。 A black matrix formed from the cured product according to claim 11.
- 請求項11に記載の硬化物から形成される着色スペーサー。 A colored spacer formed from the cured product according to claim 11.
- 請求項12に記載のブラックマトリクス又は請求項13に記載の着色スペーサーを含む画像表示装置。 An image display device comprising the black matrix according to claim 12 or the colored spacer according to claim 13.
- (A)色材、及び(B)分散剤を含有する顔料分散液であって、
前記(A)色材が(A-1)下記一般式(1)で表される化合物、その幾何異性体、その塩、またはその幾何異性体の塩である有機黒色顔料を含み、かつ、
前記(B)分散剤が4級アンモニウム塩基を官能基として有する高分子分散剤を含む顔料分散液。
[式(1)中、R1およびR6は互いに独立して水素原子、CH3、CF3、フッ素原子または塩素原子である;R2、R3、R4、R5、R7、R8、R9およびR10は他の全てから互いに独立して水素原子、ハロゲン原子、R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N=CH2、N=CHR11、N=CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11またはSO2NR11R12である;且つ、R2とR3、R3とR4、R4とR5、R7とR8、R8とR9、及びR9とR10からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合し、または酸素原子、硫黄原子、NH若しくはNR11ブリッジによって互いに結合することもできる;R11およびR12は互いに独立して、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基または炭素数2~12のアルキニル基である。] A pigment dispersion containing (A) a color material and (B) a dispersant,
The colorant (A) comprises (A-1) an organic black pigment which is a compound represented by the following general formula (1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer;
(B) A pigment dispersion containing a polymer dispersant in which the dispersant has a quaternary ammonium base as a functional group.
[In the formula (1), R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom; R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9, and R 10 are independently of each other hydrogen atoms, halogen atoms, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11. , COCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N = CH 2 , N = CHR 11 , N = CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 − , SO 2 NH 2 , S O 2 NHR 11 or SO 2 NR 11 R 12 ; and R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 7 and R 8 , R 8 and R 9 , and R 9 At least one combination selected from the group consisting of R 10 may be directly bonded to each other, or may be bonded to each other by an oxygen atom, sulfur atom, NH or NR 11 bridge; R 11 and R 12 are independently of each other; An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. ] - 前記一般式(1)において、
式中、R2、R4、R5、R7、R9およびR10は互いに独立して水素原子、フッ素原子、または塩素原子であり、R3およびR8は互いに独立して水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3HまたはSO3 -であり、R1はR6と同一であり、R2はR7と同一であり、R3はR8と同一であり、R4はR9と同一であり、R5はR10と同一である、請求項15に記載の顔料分散液。 In the general formula (1),
In the formula, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently a hydrogen atom, a fluorine atom or a chlorine atom, and R 3 and R 8 are independently a hydrogen atom, NO 2, OCH 3, OC 2 H 5, a bromine atom, a chlorine atom, CH 3, C 2 H 5 , N (CH 3) 2, N (CH 3) (C 2 H 5), N (C 2 H 5 ) 2 , α-naphthyl, β-naphthyl, SO 3 H or SO 3 — , R 1 is the same as R 6 , R 2 is the same as R 7 , and R 3 is the same as R 8 The pigment dispersion of claim 15, wherein R 4 is the same as R 9 and R 5 is the same as R 10 . - 前記高分子分散剤が、さらに3級アミンを官能基として有する、請求項15又は請求項16に記載の顔料分散液。 The pigment dispersion according to claim 15 or 16, wherein the polymer dispersant further has a tertiary amine as a functional group.
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