WO2018151079A1 - 感光性着色組成物、硬化物、着色スペーサー、画像表示装置 - Google Patents
感光性着色組成物、硬化物、着色スペーサー、画像表示装置 Download PDFInfo
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- WO2018151079A1 WO2018151079A1 PCT/JP2018/004832 JP2018004832W WO2018151079A1 WO 2018151079 A1 WO2018151079 A1 WO 2018151079A1 JP 2018004832 W JP2018004832 W JP 2018004832W WO 2018151079 A1 WO2018151079 A1 WO 2018151079A1
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- 0 *OC(COC(C=C)=O)COc(c(-c1cc(cccc2)c2cc1)c1)cc(OCC(C*C(C=C)=*)ON)c1-c1cc(cccc2)c2cc1 Chemical compound *OC(COC(C=C)=O)COc(c(-c1cc(cccc2)c2cc1)c1)cc(OCC(C*C(C=C)=*)ON)c1-c1cc(cccc2)c2cc1 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
- 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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- 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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- 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
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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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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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
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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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- 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
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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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- 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/44—Azines of the anthracene series
- C09B5/46—Para-diazines
- C09B5/48—Bis-anthraquinonediazines (indanthrone)
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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
- C09B7/00—Indigoid dyes
Definitions
- the present invention relates to a photosensitive coloring composition and the like.
- a photosensitive coloring composition that is preferably used for forming a colored spacer or the like in an image display device such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, and a color formed from the cured product
- the present invention relates to a spacer and an image display device including the colored spacer.
- Liquid crystal display utilizes the property that the arrangement of liquid crystal molecules is switched by turning on / off the voltage to the liquid crystal.
- each member constituting the cell of the LCD is often formed by a method using a photosensitive composition represented by a photolithography method. This photosensitive composition tends to form a fine structure and is easy to process a substrate for a large screen, and its application range tends to further expand in the future.
- an LCD manufactured using a photosensitive composition does not maintain the voltage applied to the liquid crystal due to the electrical characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, thereby causing the display to display. Problems such as display unevenness may occur.
- a member closer to the liquid crystal layer in a color liquid crystal display for example, a so-called columnar spacer, photospacer or the like used to keep the distance between two substrates constant in a liquid crystal panel has a great influence.
- Patent Document 1 discloses that by using a specific black pigment species, it is possible to realize a sufficiently low relative dielectric constant with excellent light-shielding properties, dispersibility, and platemaking properties.
- Patent Document 2 discloses a colored photosensitive resin composition that is excellent in elastic recovery rate, resolution, chemical resistance and satisfies the characteristics of a black matrix by using a plurality of types of organic coloring pigments. Yes.
- the colored spacers With changes in panel structure in recent years, it is necessary for the colored spacers to ensure a transmittance near 900 nm wavelength so that no light leaks even near a wavelength of 700 nm and a mark for mask alignment can be recognized during exposure. It may become.
- a method of irradiating with ultraviolet rays after creating a liquid crystal cell has been spreading. When irradiated with ultraviolet rays, there is a tendency that a part of the pigment or its treating agent decomposes to produce impurities, but even in that case, it is required to maintain sufficient electrical reliability.
- the present invention has been made in view of the above circumstances, and is a photosensitive coloring that has little light leakage around a wavelength of 700 nm, excellent light transmittance near a wavelength of 900 m, and excellent electrical reliability after ultraviolet irradiation.
- the object is to provide a composition
- a specific organic black pigment C.I. I.
- the present inventors have found that the above-mentioned problems can be solved by using Pigment Blue 60 and carbon black and setting the content ratio of the specific organic black pigment to the carbon black within a specific range. That is, the present invention has the following configurations [1] to [12].
- Photosensitive coloring containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant.
- a composition comprising: The colorant (a) is selected from the group consisting of (a1) a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound.
- the photosensitive coloring composition wherein a content ratio of the (a1) organic black pigment to 150 parts by mass of the (a3) carbon black is 150 parts by mass or more.
- R 1 and R 6 are each independently a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- An image display device comprising the colored spacer according to [11].
- a photosensitive coloring composition a cured product, and a colored spacer that have little light leakage near a wavelength of 700 nm, excellent light transmittance near a wavelength of 900 nm, and excellent electrical reliability after ultraviolet irradiation. Furthermore, an image display apparatus provided with such a colored spacer can be provided.
- FIG. 1 is a schematic view of the upper surface of the electrode substrate B used in the examples.
- FIG. 2 is a schematic side view of the liquid crystal cell for measurement used in the examples.
- FIG. 3 is a schematic diagram of an applied voltage waveform for one cycle and a schematic diagram of a measured current waveform in ion density measurement.
- (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.
- “weight average molecular weight” refers to polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography).
- the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.
- the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
- CI means a color index
- the photosensitive coloring composition of the present invention is (A) a colorant (b) an alkali-soluble resin (c) a photopolymerization initiator (d) an ethylenically unsaturated compound (e) a solvent (f) a dispersant as an essential component, and if necessary, a silane cup It includes adhesion improvers such as ring agents, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, and other compounding components. Used in a state dissolved or dispersed in a solvent.
- the colorant is (a1) a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a geometry of the compound.
- An organic black pigment containing at least one selected from the group consisting of isomer salts, (a2) C.I. I. Pigment Blue 60 and (a3) carbon black are included, and the content ratio of the (a1) organic black pigment to 100 parts by mass of (a3) carbon black is 150 parts by mass or more.
- each component will be described in detail.
- the (a) colorant in the photosensitive coloring composition of the present invention contains the following (a1), (a2) and (a3) as essential components.
- (A1) An organic black containing at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Pigment (a2) C.I. I. Pigment Blue 60 (A3) Carbon black Among these pigments, (a1) and (a2) are organic pigments, and (a3) is an inorganic pigment.
- the colorant contained in the photosensitive coloring composition of the present invention includes (a1) a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and An organic black pigment containing at least one selected from the group consisting of salts of geometric isomers of the compound (hereinafter sometimes abbreviated as “(a1) organic black pigment”) is contained as an essential component.
- (a1) organic black pigment By containing an organic black pigment, it is thought that light-shielding property is ensured, the fall of the voltage holding rate of a liquid crystal is suppressed, and the shape and level
- 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 the general formula (I) and geometric isomers of the compound have the following core structure (however, substituents in the structural formula are omitted), and the trans-trans isomer is probably the most It is stable.
- the compound represented by general formula (I) When the compound represented by general formula (I) 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 A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium, or trialkylammonium, a quaternary ammonium such as tetraalkylammonium, or an organometallic complex. Further, when the geometric isomer of the compound represented by the general formula (I) is anionic, it is preferably a similar salt.
- a metal, organic, inorganic or metal organic cation specifically an alkali metal, alkaline earth metal A salt compensated by a transition metal, a tertiary ammonium such as primary ammonium, secondary ammonium, or trialkylammonium, a quaternary ammonium such as tetraalkylam
- R 2 , R 4 , R 5 , R 7 , R 9 and R 10 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
- R 3 and R 8 are preferably 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 — , more preferably a hydrogen atom or SO 3 H.
- R 1 and R 6 are each independently preferably a hydrogen atom, CH 3 or CF 3 , and more preferably a hydrogen atom.
- R 1 and R 6, R 2 and R 7, R 3 and R 8, R 4 and R 9, which and R 5 and at least one combination selected from the group consisting of R 10 are identical substituents More preferably, R 1 is the same substituent as R 6 , R 2 is the same substituent as R 7 , R 3 is the same substituent as R 8 , and R 4 is R 9. And R 5 is the same substituent as R 10 .
- 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 -An yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a 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.
- the (a1) organic black pigment is at least one selected from the group consisting of the compound represented by the general formula (I), the geometric isomer of the compound, the salt of the compound, and the salt of the geometric isomer of the compound.
- a seed may be included, but a plurality of them may be included.
- the (a1) organic black pigment includes a compound represented by the general formula (I), a geometric isomer of the compound, a salt of the compound, and a geometric isomer of the compound from the viewpoints of light shielding properties and electrical reliability. It is preferable that it consists of at least 1 sort (s) chosen from the group which consists of these salts.
- the (a1) organic black pigment is preferably a compound represented by the following general formula (I-1) and / or a geometric isomer of the above compound, and more preferably represented by the following general formula (I-1). It is a compound.
- organic black pigments include Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) under the trade name.
- This organic black pigment is preferably used after being dispersed by a dispersant, a solvent and a method described later.
- the sulfonic acid derivative (sulfonic acid substituted product) of the compound represented by the general formula (I) is present, particularly the sulfonic acid derivative of the compound represented by the general formula (I-1) is present at the time of dispersion, Since dispersibility and storage stability may be improved, it is preferable that the (a1) organic black pigment further contains these sulfonic acid derivatives.
- the (a1) organic black pigment preferably further contains a compound represented by the following general formula (I-2) and / or a geometric isomer of the compound.
- the (a) colorant contained in the photosensitive coloring composition of the present invention includes (a2) C.I. I. Pigment Blue 60 is contained as an essential component.
- the (a1) organic black pigment has a high transmittance in the vicinity of a wavelength of 650 to 750 nm, and the light shielding property in the wavelength region is insufficient.
- CI Pigment Blue 60 has an absorption band in the wavelength region, (a2) C.I. I. It is considered that the transmittance in the wavelength region can be reduced by using together with Pigment Blue 60.
- C.I. I. Pigment Blue 60 is C.I. I.
- the transmittance near 300 to 400 nm is high, and it is easy to control the shape and level difference of the colored spacer by suppressing the absorption of ultraviolet rays.
- the voltage holding ratio is high, and the ion density is low.
- the absorption of ultraviolet rays is small, it is considered that there is little degradation or elution of impurities due to ultraviolet irradiation, and there is little decrease in voltage holding ratio or ion density even after ultraviolet irradiation for improving liquid crystal alignment. Excellent reliability.
- the (a) colorant contained in the photosensitive coloring composition of the present invention contains (a3) carbon black as an essential component.
- (A3) Carbon black has an absorption spectrum entirely at all wavelengths in the visible region and has a low transmittance. Therefore, (a1) an organic black pigment, (a2) C.I. I.
- a3 By containing carbon black in addition to Pigment Blue 60 (a3), it is possible to achieve high light-shielding properties, to suppress light leakage, and to reduce the content of the colorant with respect to the total solid content. Therefore, it is considered that high electrical reliability can be secured.
- Examples of carbon black include the following carbon black.
- the surface pH of the carbon black used in the present invention is not particularly limited, but is preferably 9 or less, more preferably 7 or less, still more preferably 5 or less, and particularly preferably 4 or less. By setting it to the upper limit or less, the dispersant tends to adhere and the dispersibility tends to be good.
- the pH of the surface of carbon black is preferably as low as possible, but is usually 2 or more. The pH of the carbon black surface is measured by dispersing the carbon black powder in water and measuring the aqueous pH of the dispersion.
- the average particle size of carbon black is preferably 8 nm or more, more preferably 17 nm or more, further preferably 21 nm or more, more preferably 100 nm or less, more preferably 65 nm or less, still more preferably 40 nm or less, and particularly preferably 32 nm or less.
- the average particle diameter of carbon black in the present invention means a number average particle diameter. In general, the average particle size of carbon black is obtained by particle image analysis by taking several fields of photographs taken at tens of thousands of times by electron microscope observation, and measuring about 2000 to 3000 particles of these photographs with an image processor. It is done.
- Carbon black coated with resin may be used.
- Use of carbon black coated with a resin has the effect of improving adhesion to a glass substrate and volume resistance.
- carbon black coated with the resin for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
- Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
- the total content of Na and Ca is preferably 100 ppm or less.
- Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe. Ashes are contained in the composition.
- Na and Ca are generally contained in a few hundred ppm or more, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electricity Tend to prevent mechanical short circuit.
- the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is small, it is possible to cover fine units. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption is 140 mL / 100 g or less. By setting it within the above range, a coating film having good light shielding properties tends to be obtained.
- the method for preparing carbon black coated with resin is not particularly limited. For example, after appropriately adjusting the blending amount of carbon black and resin, After mixing and stirring a resin solution obtained by mixing a resin and a solvent such as cyclohexanone, toluene, xylene and the like, and a suspension obtained by mixing carbon black and water, carbon black and water are separated, 1. A method in which the composition obtained by removing water and heating and kneading is formed into a sheet, pulverized and then dried; A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and the resin, and then the resulting granular material is separated and heated to remove the remaining solvent and water; 3.
- a carboxylic acid such as maleic acid or fumaric acid is dissolved in the above exemplified solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and then a resin is added thereto.
- dry blending method A reactive group-containing monomer component constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension.
- a method of adding carbon black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.
- the type of resin to be coated is not particularly limited, but a synthetic resin is generally used, and a resin having a benzene ring in the structure has the same action as an amphoteric surfactant, dispersibility and It is preferable from the viewpoint of dispersion stability.
- Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene.
- Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, can be used.
- the amount of the coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and resin. There exists a tendency which can make coating
- the carbon black thus coated with a resin can be used as a coloring agent for a colored spacer according to a conventional method, and a color filter having this colored spacer as a constituent element can be prepared by a conventional method.
- a coloring agent for a colored spacer according to a conventional method
- a color filter having this colored spacer as a constituent element can be prepared by a conventional method.
- a colored spacer having a high light shielding rate and a low surface reflectance can be formed at a low cost.
- Ca and Na can be contained in the carbon black.
- the (a) colorant contained in the photosensitive coloring composition of the present invention contains other colorants such as other pigments and other dyes in addition to the pigments (a1), (a2) and (a3). You may go out.
- colorants of each color such as red, orange, blue, purple, green, yellow, can be used.
- black pigments other than the above (a1) and (a3) can also be used.
- organic pigments it is preferable to use organic pigments from the viewpoint of suppressing the decrease in the voltage holding ratio of the liquid crystal and suppressing the absorption of ultraviolet rays to easily control the shape and steps of the colored spacer. .
- the chemical structure of other pigments is not particularly limited, but various organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene are used. Inorganic pigments can also be used. Hereinafter, specific examples of usable organic pigments are indicated by pigment numbers.
- C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272, more preferably C.I. I. Pigment red 177, 209, 224, 254, 272, particularly preferably C.I. I. Pigment red 177, 254, 272.
- a red pigment having a low ultraviolet absorptivity I. Pigment Red 254 and 272 are more preferable.
- C.I. I. Pigment Orange 1 As orange (orange) pigments, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
- C.I. I. Pigment Orange 13, 43, 64, and 72 are preferable.
- I. Pigment Orange 64 and 72 are more preferable, and C.I. I. Pigment Orange 64 is more preferable.
- 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, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15: 6, 16 is preferable.
- Examples of purple pigments include 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 preferable, and in the case of curing with ultraviolet rays, it is preferable to use a violet pigment having a low ultraviolet absorption rate.
- I. Pigment Violet 29 is more preferable.
- From the viewpoint of light shielding properties C.I. I. Pigment Violet 29 is preferable.
- organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
- green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
- yellow pigments 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 pigments and / or purple pigments are preferable from the viewpoint of light shielding properties and reliability, purple pigments are more preferable from the viewpoint of light shielding properties, and C.I. I. Pigment Violet 29 is more preferable.
- black pigments other than (a1) and (a3) include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene black.
- Other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
- 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.
- the (a1), (a2), (a3), and other pigments are used in a dispersed manner so that the average particle size is usually 1 ⁇ m or less, preferably 0.5 ⁇ m or less, more preferably 0.25 ⁇ m or less. Is preferred.
- 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). The particle size is measured by fully diluting the photosensitive coloring composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument, According to concentration) and measured at 25 ° C.
- the (b) alkali-soluble resin used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group.
- an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy resin, or a carboxyl group-containing resin is used.
- a urethane resin, a novolac resin, a polyvinylphenol resin, and the like can be mentioned.
- (b1) epoxy (meth) acrylate resin (b2) acrylic copolymer resin is preferably used from the viewpoint of excellent plate making properties. These can be used individually by 1 type or in mixture of multiple types.
- An epoxy (meth) acrylate resin comprises an epoxy compound (epoxy resin) and an ⁇ , ⁇ -unsaturated monocarboxylic acid and / or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety. It is a resin obtained by reacting a hydroxyl group produced by the reaction with a compound having two or more substituents capable of reacting with a hydroxyl group such as a polybasic acid and / or its anhydride.
- the compound having two or more substituents capable of reacting with the hydroxyl group is reacted, and then the polybasic acid and / or anhydride thereof is reacted.
- Resins obtained by reacting products are also included in the (b1) epoxy (meth) acrylate resin.
- the resin obtained by making the carboxyl group of the resin obtained by the said reaction react with the compound which has a functional group which can react further is also contained in the said (b1) epoxy (meth) acrylate type resin.
- the epoxy (meth) acrylate resin does not substantially have an epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but an epoxy compound (epoxy resin) is a raw material.
- (meth) acrylate” is a representative example, it is named in accordance with conventional usage.
- Examples of the (b1) epoxy (meth) acrylate resin used in the present invention include the following epoxy (meth) acrylate resin (b1-1) and / or epoxy (meth) acrylate resin (b1-2) (hereinafter referred to as “carboxyl”).
- Group-containing epoxy (meth) acrylate resin ” may be referred to from the viewpoint of developability and reliability.
- the epoxy resin includes the raw material compound before the resin is formed by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and epihalohydrin react.
- the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
- the types of epoxy resins used as raw materials are cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolak type
- An epoxy resin, an epoxy resin that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and an epihalohydrin, an adamantyl group-containing epoxy resin, a fluorene type epoxy resin, and the like can be suitably used. Those having an aromatic ring in the main chain can be suitably used.
- the epoxy resin examples include, for example, a bisphenol A type epoxy resin (for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, etc. manufactured by Mitsubishi Chemical Corporation). ), Epoxy resin 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 bisphenol A type epoxy resin for example, “jER (registered trademark, the same applies hereinafter) 828”, “jER1001”, “jER1002”, “jER1004”, etc. manufactured by Mitsubishi Chemical Corporation.
- Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin for example, “NER-1302” manufactured by Nippon Kayaku Co., Ltd.
- NC-3000 ”and epoxy resin represented by the following general formula (B4) include“ ESF-300 ”manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- a is an average value and represents a number from 0 to 10
- each R 111 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 3 to 10 carbon atoms.
- a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group is represented.
- a plurality of R 111 present in one molecule may be the same or different from each other.
- b is an average value and represents a number from 0 to 10
- R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 3 to 10 carbon atoms.
- a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group is represented.
- a plurality of R 121 present in one molecule may be the same or different from each other.
- X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, one or more adamantane structures are included in the molecular structure.
- c represents 2 or 3.
- R 131 to R 134 and R 135 to R 137 are each independently an adamantyl group optionally having a substituent, a hydrogen atom, a substituent Represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group, and * represents a bond.
- 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 142 144 each independently represents an alkylene group having 1 to 4 carbon atoms
- x and y each independently represents an integer of 0 or more.
- an epoxy resin represented by any one of the general formulas (B1) to (B4) it is preferable to use an epoxy resin represented by any one of the general formulas (B1) to (B4).
- Examples of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, (meta ) Monocarboxylic acid such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, cyano substituent of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth) acryl
- an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
- a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
- an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can.
- esterification catalyst used here tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .
- each component of the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst is selected and used one by one. Or two or more of them may be used in combination.
- 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.
- the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is not less than the above lower limit, it is possible to suppress the shortage of the amount of unsaturated groups introduced. There is also a tendency that the reaction with the basic acid and / or its anhydride tends to be sufficient. On the other hand, when the amount is not more than the above upper limit, it is possible to suppress the remaining unreacted ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and to have good curing characteristics. The tendency to be easy to do is recognized.
- 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 anhydride component thereof 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,
- the degree is preferably in the range of 20 to 140 mgKOH / g.
- polyfunctional alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, and the like may be added during the addition reaction of the polybasic acid and / or anhydride thereof to introduce a multi-branched structure. Good.
- a carboxyl group-containing epoxy (meth) acrylate-based resin is usually a polybasic acid as a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group. And / or an anhydride thereof, or a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, / Or its anhydride and polyfunctional alcohol are mixed and then heated.
- 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.
- Examples of the epoxy (meth) acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955, in addition to the above-mentioned ones.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, more preferably 3000 or more. More preferably, it is 4000 or more, particularly preferably 5000 or more, and usually 10,000 or less, preferably 8000 or less, more preferably 7000 or less.
- GPC gel permeation chromatography
- the combination of the upper limit and the lower limit is preferably 1000 to 10000, more preferably 1500 to 8000, further preferably 2000 to 8000, still more preferably 3000 to 8000, particularly preferably 4000 to 8000, and most preferably 5000 to 7000.
- the combination of the upper limit and the lower limit is preferably 1000 to 10000, more preferably 1500 to 8000, further preferably 2000 to 8000, still more preferably 3000 to 8000, particularly preferably 4000 to 8000, and most preferably 5000 to 7000.
- the combination of the upper limit and the lower limit is preferably 1000 to 10000, more preferably 1500 to 8000, further preferably 2000 to 8000, still more preferably 3000 to 8000, particularly preferably 4000 to 8000, and most preferably 5000 to 7000.
- the combination of the upper limit and the lower limit is preferably 1000 to 10000, more preferably 1500 to 8000, further preferably 2000 to 8000, still more preferably 3000 to 8000, particularly preferably 4000 to 8000, and most preferably 5000
- the acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 120 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable.
- the amount is not less than the lower limit value, moderate development solubility tends to be obtained, and when the value is not more than the upper limit value, the development tends to be excessive and the film dissolution tends to be suppressed.
- the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, further preferably 40 to 100 mgKOH / g, and particularly preferably 50 to 100 mgKOH / g.
- the chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate resin (hereinafter referred to as a partial structure represented by the following general formula (b1-I)) May be abbreviated as “(b1-I) epoxy (meth) acrylate resin”) and / or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b1-II) ( Hereinafter, it may be preferable to contain “(b1-II) epoxy (meth) acrylate resin”.
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents a divalent hydrocarbon group which may have a substituent
- * represents a bond.
- the benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent.
- each R 13 independently represents a hydrogen atom or a methyl group
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represents an integer of 0 to 2
- * represents a bond.
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents a divalent hydrocarbon group which may have a substituent
- * represents a bond.
- the benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent.
- R 12 represents a divalent hydrocarbon group which may have a substituent.
- the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility. On the other hand, from the viewpoint of reducing the penetration of the developer into the exposed area, a ring-shaped one is preferable.
- the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the combination of the upper limit and the lower limit is preferably 1-20, more preferably 3-15, and still more preferably 6-10.
- divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. .
- a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
- divalent branched aliphatic group examples include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less.
- divalent cyclic aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom.
- a group in which two are removed Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the combination of the upper limit and the lower limit is preferably 4 to 20, more preferably 5 to 15, and further preferably 6 to 10.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having two free valences, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
- the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole having two free valences.
- Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of development solubility.
- divalent aliphatic groups and one or more divalent aromatic ring groups are linked
- one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
- the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
- the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of simplicity of synthesis.
- R 11 and R 12 have the same meanings as those in the formula (b1-I), R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond.
- R X represents a hydrogen atom or a polybasic acid residue, and * represents a bond.
- the benzene ring in formula (b1-I-1) may be further substituted with an arbitrary substituent.
- the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
- Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid Examples thereof include one or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- (B1-I) an epoxy (meth) included in the acrylate resins in a molecule, a partial structure represented by the formula (b1-I-1) may be one kind or two or more species, for example, R X is The thing of a hydrogen atom and the thing of R ⁇ X > may be a polybasic acid residue may be mixed.
- the number of partial structures represented by the formula (b1-I) contained in one molecule of (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more and 3 or more. More preferably, it is preferably 20 or less, and more preferably 15 or less. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 20, and more preferably 3 to 15.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is further preferable, and 8000 or less is particularly preferable. .
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, still more preferably 2000 to 10000, still more preferably 3000 to 10000, particularly preferably 4000 to 80000, and most preferably 5000 to 8000.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, still more preferably 2000 to 10000, still more preferably 3000 to 10000, particularly preferably 4000 to 80000, and most preferably 5000 to 8000.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, still more preferably 2000 to 10000, still more preferably 3000 to 10000, particularly preferably 4000 to 80000, and most preferably 5000 to 8000.
- the acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and 50 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 130 mgKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, still more preferably 40 to 100 mgKOH / g, still more preferably 50 to 100 mgKOH / g, and 80 to 100 mgKOH / g. Particularly preferred is g.
- each R 13 independently represents a hydrogen atom or a methyl group
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represents an integer of 0 to 2
- * represents a bond.
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and still more preferably 8 to 20.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the photosensitive coloring composition.
- the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, preferably 4 or less. Is more preferable. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 4.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, preferably 30 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
- aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, Examples include fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
- the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
- the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less.
- the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
- the combination of the upper limit and the lower limit is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15.
- divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. .
- a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
- divalent branched aliphatic group examples include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group.
- the number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the value is not less than the lower limit value, a strong film tends to be obtained and the substrate adhesion tends to be good.
- the value is not more than the upper limit value, it is easy to suppress deterioration of sensitivity and film loss during development, and resolution. Tend to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the divalent aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
- a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
- the aromatic hydrocarbon ring group for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring having two free valences, Examples include acenaphthene ring, fluoranthene ring, fluorene ring and the like.
- the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.
- the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole having two free valences.
- Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferable from the viewpoint of development solubility.
- divalent aliphatic groups and one or more divalent aromatic ring groups are linked
- one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
- the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
- the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include those represented by the formulas (b1-IA) to (b1-IF). And the like.
- the group represented by the formula (b1-IC) is preferable from the viewpoint of skeleton rigidity and membrane hydrophobicity.
- the bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited. For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. And a mode in which a cyclic hydrocarbon group which is a side chain including one of the carbon atoms of the aliphatic group is formed.
- R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent.
- Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing penetration of the developer into the exposed portion.
- the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the amount is not less than the lower limit value, a strong film is easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. It is easy to suppress the film loss at the time, and the resolution tends to be improved.
- the combination of the upper limit and the lower limit is preferably 1-20, more preferably 3-15, and still more preferably 6-10.
- divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group and the like. .
- a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
- divalent branched aliphatic group examples include the divalent linear aliphatic group described above, and the side chain includes a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less.
- By setting the lower limit value or more a strong film tends to be obtained and the substrate adhesion tends to be good.
- By setting the upper limit value or less it is easy to suppress deterioration of sensitivity and film reduction during development, and resolution. Tend to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 12, and more preferably 2 to 10.
- divalent cyclic aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene, and a hydrogen atom.
- a group in which two are removed Among these, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable from the viewpoint of skeleton rigidity.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- m and n each independently represents an integer of 0 to 2.
- m and n are preferably 0.
- m and n are preferably 1 or more from the viewpoints of patterning suitability and surface roughness.
- the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesion to the substrate.
- R 13 , R 15 , R 16 , m and n are as defined in the above formula (b1-II), and R ⁇ is a monovalent optionally having substituent (s).
- p is an integer of 1 or more, and * represents a bond.
- the benzene ring in formula (b1-II-1) may be further substituted with an arbitrary substituent.
- R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and further preferably 2 to 3.
- the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, and particularly preferably 8 to 15.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferable from the viewpoint of strong film characteristics.
- the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the lower limit value or more By setting it to the lower limit value or more, a strong film is likely to be obtained and surface roughness tends to be less likely to occur, and by setting the upper limit value or less, patterning characteristics tend to be good.
- the combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.
- aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
- a fluorene ring is preferable from the viewpoint of development solubility.
- Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
- P represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less.
- the combination of the upper limit and the lower limit is preferably 1 to 3, and more preferably 2 to 3.
- R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.
- the benzene ring in formula (b1-II-1) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
- partial structure represented by the general formula (b1-II) is a partial structure represented by the following general formula (b1-II-2) from the viewpoints of skeleton rigidity and membrane hydrophobization. Is preferred.
- R 13 , R 15 , R 16 , m and n have the same meanings as those in formula (b1-II), and R ⁇ may be a divalent group which may have a substituent.
- the cyclic hydrocarbon group of * is represented, * represents a bond.
- the benzene ring in formula (b1-II-2) may be further substituted with an arbitrary substituent.
- R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. It is easy to obtain a strong film by making the lower limit value or more, and there is a tendency that surface roughness is less likely to occur, and it is easy to suppress deterioration of sensitivity and film loss at the time of development by making the upper limit value or less. The resolution tends to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
- carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable.
- the lower limit value or more there is a tendency to suppress film deterioration during development.
- the upper limit value or less it is easy to suppress deterioration in sensitivity and film reduction during development, and resolution is improved.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30.
- aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
- an adamantane ring is preferred from the viewpoint of film reduction during development and resolution.
- the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less.
- the lower limit value or more By setting the lower limit value or more, a strong film is likely to be obtained, and there is a tendency that surface roughness is less likely to occur, and by setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film loss, and resolution. Tend to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and further preferably 20 or less.
- 15 or less is particularly preferable.
- the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.
- aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
- a fluorene ring is preferable from the viewpoint of developability.
- Examples of the substituent that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an amyl group, Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an iso-amyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Among these, unsubstituted is preferable from the viewpoint of simplicity of synthesis.
- R beta is a divalent aliphatic cyclic group, and more preferably a divalent adamantane ring group.
- R beta is a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
- the benzene ring in formula (b1-II-2) may be further substituted with an arbitrary substituent.
- substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited, either one or two or more.
- two benzene rings may be connected via a substituent.
- Examples of the substituent in this case include divalent groups such as —O—, —S—, —NH—, —CH 2 — and the like. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics. Moreover, it is preferable that it is methyl group substitution from a viewpoint of making it hard to produce film reduction.
- the partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the remaining film ratio and patterning characteristics. .
- R 13 , R 14 , R 15 , R 16 , m and n are as defined in the formula (b1-II), and R Z represents a hydrogen atom or a polybasic acid residue.
- the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Incidentally, further another OH group is divided, may be shared with R Z in other molecules of the formula (b1-II-3), i.e., a plurality of expressions through the R Z (b1 -II-3) may be linked.
- Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
- One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are more preferable.
- (B1-II) epoxy (meth) included in the acrylate resins in one molecule wherein the partial structure represented by formula (b1-II-3) may be one kind or two or more species, for example, R Z is and that of hydrogen atoms, may be mixed those R Z is a polybasic acid residue.
- the number of partial structures represented by the formula (b1-II) contained in one molecule of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more and 3 or more. More preferably, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the lower limit value or more By setting the lower limit value or more, a strong film is likely to be obtained, and there is a tendency that surface roughness is less likely to occur, and by setting the upper limit value or less, it is easy to suppress deterioration of sensitivity and film loss, and resolution. Tend to improve.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 3 to 10.
- the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more. Moreover, 30000 or less is preferable, 20000 or less is more preferable, 10,000 or less is more preferable, 7000 or less is further more preferable, 5000 or less is especially preferable. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at most the upper limit value, a strong film is likely to be obtained and surface roughness tends not to occur.
- the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1000 to 20000, still more preferably 2000 to 10,000, still more preferably 2000 to 7000, and particularly preferably 2000 to 5000.
- the acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and more preferably 60 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 100 mgKOH / g or more is most preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, and 120 gKOH / g or less is more preferable.
- the combination of the upper limit and the lower limit is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, still more preferably 40 to 150 mgKOH / g, still more preferably 60 to 120 mgKOH / g, and 80 to 120 mgKOH / g. Particularly preferred is g.
- Epoxy (meth) acrylate resins may be used singly or as a mixture of two or more resins. Moreover, you may replace and use a part of above-mentioned epoxy (meth) acrylate type resin for another binder resin. That is, you may use together an epoxy (meth) acrylate type resin and another binder resin.
- the proportion of the epoxy (meth) acrylate resin in the alkali-soluble resin (b) is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. Is more preferably 80% by mass or more, and usually 100% by mass or less.
- the combination of the upper limit and the lower limit is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, further preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.
- binder resin which can be used together with an epoxy (meth) acrylate type resin, What is necessary is just to select from resin normally used for the photosensitive coloring composition.
- all other binder resins may be used alone or in combination of two or more.
- (b) alkali-soluble resin it is preferable to use (b2) an acrylic copolymer resin from the viewpoint of compatibility with pigments, dispersants, and the like, and those described in Japanese Patent Application Laid-Open No. 2014-137466. It can be preferably used.
- acrylic copolymer resin examples include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylene. And a copolymer with an unsaturated monomer (hereinafter referred to as “unsaturated monomer (b2-2)”).
- Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid , Unsaturated dicarboxylic acids such as citraconic acid, citraconic anhydride, and mesaconic acid or their anhydrides; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as ⁇ -carboxypolycaprolactone mono (meth) acrylate and the like. ) Acrylate; p-vinylbenzoic acid and the like. These unsaturated monomers (b2-1) can be used alone or in admixture of two or more.
- Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
- N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide
- Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;
- Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
- Examples thereof include a macromonomer having a mono (meth) acryloyl group at the terminal of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane and the like.
- These unsaturated monomers (b2-2) can be used alone or in admixture of two or more.
- the copolymerization ratio of unsaturated monomer (b2-1) in the copolymer is preferably Is 5 to 50% by mass, more preferably 10 to 40% by mass.
- copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, Japanese Patent Application Laid-Open No. 7-140654 and Japanese Patent Application Laid-Open No. 8-259876.
- No. 1 Japanese Laid-Open Patent Publication No. 10-31308, Japanese Laid-Open Patent Publication No. 10-300922, Japanese Laid-Open Patent Publication No. 11-174224, Japanese Laid-Open Patent Publication No. 11-258415, Japanese Laid-Open Patent Publication No. 2000-56118.
- copolymers disclosed in Japanese Patent Application Laid-Open No. 2004-101728 are examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include, for example, Japanese Patent Application Laid-Open No. 7-140654 and Japanese Patent Application Laid-Open No. 8-259876.
- No. 10-313008 Japanese Laid-Open Patent Publication No. 10-300922
- the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method.
- Japanese Patent Application Laid-Open No. 2003-222717 The structure, Mw, and Mw / Mn can be controlled by the methods disclosed in Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 2007/029871, and the like.
- 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.
- the photopolymerization initiator include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197; Japanese Patent Application Laid-Open No.
- 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
- hexaarylbiimidazole 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′- And methoxyphenyl) -4,5-diphenylimidazole dimer.
- halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [ ⁇ - (2 ′-(6 ′′ -benzofuryl) vinyl)]-1,3,4-oxadiazole, And 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
- halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (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
- an oxime ester compound is particularly effective in terms of sensitivity and plate-making property.
- an alkali-soluble resin containing a phenolic hydroxyl group is used, the oxime ester compound particularly excellent in such sensitivity is used.
- Compounds are useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in the structure, so they are highly sensitive in a small amount and stable against thermal reactions. It is possible to obtain a highly sensitive photosensitive coloring composition in a small amount.
- Examples of the oxime ester compound include compounds represented by the following general formula (IV).
- R 21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group
- R 21b represents an aromatic ring
- R 22a represents an optional alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.
- the number of carbon atoms of the alkyl group in R 21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. It is.
- Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
- the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 2 to 15, and further preferably 2 to 10.
- alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl.
- Examples of the aromatic ring group for R 21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and further preferably 12 or less.
- the combination of the upper limit and the lower limit is preferably 5 to 30, more preferably 5 to 20, and further preferably 5 to 12.
- aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable from the viewpoint of developability.
- substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked.
- R 21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent. preferable.
- R 21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group.
- an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.
- an optionally substituted diphenyl sulfide group is preferable.
- the number of carbon atoms of the alkanoyl group in R 22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, from the viewpoint of solubility in a solvent or sensitivity. 10 or less, more preferably 5 or less.
- the combination of the upper limit and the lower limit is preferably 2 to 20, more preferably 2 to 15, further preferably 3 to 10, and particularly preferably 3 to 5.
- Specific examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.
- alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the substituent may be unsubstituted. Is preferred.
- the number of carbon atoms of the aryloyl group in R 22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in a solvent or sensitivity. 10 or less.
- Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
- the combination of the upper limit and the lower limit is preferably 7 to 20, more preferably 8 to 15, and still more preferably 8 to 10.
- the substituent that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group.
- R 22a is preferably an alkanoyl group which may have a substituent, more preferably an unsubstituted alkanoyl group, and further preferably an acetyl group.
- a photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more type.
- a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be blended with the photopolymerization initiator as necessary for the purpose of increasing the sensitivity.
- sensitizing dyes xanthene dyes described in JP-A-4-221958, JP-A-4-219756, JP-A-3-239703, JP-A-5-289335
- amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone.
- Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) ) Benzothiazole, 2- (p-diethi) Ruaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazol
- polymerization accelerator examples include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. It is done.
- a polymerization accelerator may be used individually by 1 type, or may use 2 or more types together.
- the photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound.
- the ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.
- a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly desirable.
- the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. There exists a tendency for it to become high sensitivity by setting it as the said lower limit or more, and there exists a tendency for the solubility to a solvent to improve by setting it as the said upper limit or less.
- the combination of the upper limit and the lower limit is preferably 2 to 8, more preferably 4 to 7, and further preferably 5 to 7.
- the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, and an aromatic polyhydroxy compound.
- 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 (made by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (made by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- (meth) acrylic acid alkyl ester as (d) ethylenically unsaturated compound, and it is more preferable to use dipentaerythritol hexaacrylate. These may be used alone or in combination of two or more.
- the photosensitive coloring composition of the present invention contains (e) a solvent.
- (E) By including a solvent, (a) the colorant can be dissolved or dispersed in the solvent, and the coating becomes easy.
- the photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and necessary.
- Various other materials used according to the above are used in a state dissolved or dispersed in a solvent.
- organic solvents are preferable from the viewpoints of dispersibility and coatability.
- organic solvents those having a boiling point in the range of 100 to 300 ° C. are preferably selected from the viewpoint of applicability, and those having a boiling point in the range of 120 to 280 ° C. are more preferable.
- the boiling point here means the boiling point at a pressure of 101.25 hPa, and the same applies to the boiling points hereinafter.
- 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-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl Ether, tri Chi glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol mono
- 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
- organic solvents corresponding to the above include mineral spirits, Valsol # 2, Apco # 18 solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cerosolve” is a registered trademark, the same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (any Product name). These organic solvents may be used alone or in combination of two or more.
- an organic solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.
- glycol alkyl ether acetates are preferred from the viewpoints of good balance in coating properties, surface tension, and the like, and relatively high solubility of 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 photosensitive coloring 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 photosensitive coloring composition is difficult to dry, but 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 or solidification of a colorant or the like 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. preferable.
- the drying temperature of the composition Tends to be able to suppress slowing down and to prevent problems such as tact failure in the vacuum drying process and pre-baked pin marks
- 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.
- a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable.
- a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, disperses the pigment.
- a basic functional group such as a primary, secondary or tertiary amino group
- a quaternary ammonium base such as pyridine, pyrimidine or pyrazine
- polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers.
- examples thereof include a system dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.
- a dispersant examples include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK Chemie), Disparon (registered trademark, manufactured by Enomoto Kasei), and SOLPERSE. (Registered trademark, manufactured by Lubrizol Corp.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
- the combination of the upper limit and the lower limit is preferably 700 to 100,000, more preferably 1000 to 50,000.
- the dispersant preferably contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group. It is particularly preferable to include it. 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-based and acrylic polymer dispersants examples include DISPERBYK160 to 166, 182 series (both urethane-based), DISPERBYK2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by BYK Chemie).
- Specific examples of preferred chemical structures as urethane polymer dispersants include, for example, a polyisocyanate compound, 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 active hydrogen with a compound having a tertiary amino group. 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.
- a quaternizing agent such as benzyl chloride
- 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 a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds has 1 to 25 carbon atoms. And those obtained by alkoxylation with an alkyl group and a mixture of two or more of these.
- 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. The mixture of 2 or more types of these is mentioned.
- Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate.
- 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 10000, preferably 500 to 6000, more preferably 1000 to 4000.
- 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-based polymer dispersant is 10 to 200 of a compound 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. Parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of the compound having an active hydrogen and a tertiary amino group in the same molecule. Part by mass.
- 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 amount is not less than the lower limit value, the dispersing ability tends to be good, and when the amount is not more than the upper limit value, a decrease in developability tends to be suppressed.
- the weight average molecular weight (Mw) of the urethane 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. Dispersibility and dispersion stability tend to be good when the lower limit is exceeded, and lowering of solubility and dispersibility tends to be easily suppressed when the upper limit is reached.
- an acrylic polymer dispersant 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 of the polymer and 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.
- the content rate 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.
- the / B block ratio is preferably 1/99 to 80/20, and particularly preferably 5/95 to 60/40 (mass ratio), and within this range, a balance between dispersibility and storage stability can be ensured.
- the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. There exists a tendency which can ensure favorable dispersibility by making it in the range.
- 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 combination of the upper limit and the lower limit is preferably 10 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and 50 to 75 mgKOH / g.
- 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.
- the combination of the upper limit and the lower limit is preferably 10 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g, and further preferably 50 to 75 mgKOH / g.
- 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 amine value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but generally it is preferably lower, usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. There exists a tendency which can ensure favorable dispersibility by setting it as the said range.
- the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is represented by the following formula (i). It is preferable to have a repeating unit (hereinafter sometimes 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 linkage.
- a 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, preferably 10 or less, The following is more preferable.
- the combination of the upper limit and the lower limit is preferably 1 to 10, and more preferably 1 to 6.
- 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.
- a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either 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.
- the combination of the upper limit and the lower limit is preferably 6 to 16, and more preferably 6 to 12.
- 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.
- the combination of the upper limit and the lower limit is preferably 7 to 16, and more preferably 7 to 12.
- Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
- a phenylmethyl group and a phenylethyl group Group a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
- R 31 ⁇ R 33 are each independently an alkyl group, or an aralkyl group, specifically, methyl group independently R 31 and R 33 are each, or ethyl R 32 is preferably a phenylmethylene group or a phenylethylene group, more preferably R 31 and R 33 are methyl groups, and R 32 is a phenylmethylene group.
- the repeating unit represented by the following formula (ii) (hereinafter referred to as “repeating unit (ii)”) It is preferable to have.
- 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 in the above formula (ii) those exemplified as R 31 to R 33 in 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 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.
- 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, A —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). Is a —COO—R 44 — group.
- the counter anion of Y - The, Cl -, Br -, I -, ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - , and the like.
- the content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) and the 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 combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, and particularly preferably 30 to 40 mol%.
- 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 combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 20 mol%, and particularly preferably 10 to 15 mol%.
- 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 combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.
- 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 1 to It is an integer of 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.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 6.
- 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.
- a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either 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 combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
- 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 combination of the upper limit and the lower limit is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and further preferably 4 to 10 mol%.
- 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.
- 39 is a hydrogen atom or a methyl group.
- the number of carbon atoms of the alkyl group which 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.
- the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 8, and further preferably 4 to 8.
- 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.
- a methyl group, an ethyl group, a propyl group, and a butyl group are exemplified. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either 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.
- the combination of the upper limit and the lower limit is preferably 6 to 16, more preferably 6 to 12, and further preferably 6 to 8.
- 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.
- the combination of the upper limit and the lower limit is preferably 7 to 16, more preferably 7 to 12, and further preferably 7 to 10.
- Specific examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.
- a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenyl group It is preferably a butyl group, more preferably a phenylmethyl group or a phenylethyl group.
- R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group.
- substituents that the alkyl group may have in R 38 include a halogen atom and an alkoxy group.
- 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 combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and further preferably 50 to 70 mol%.
- 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 photosensitive coloring composition of the present invention includes an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, and a mercapto compound.
- an adhesion improver such as a silane coupling agent, a surfactant (applicability improver), a pigment derivative, a photoacid generator, a crosslinking agent, and a mercapto compound.
- additives such as a polymerization inhibitor, a development improver, an ultraviolet absorber, and an antioxidant can be appropriately blended.
- the photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate.
- an adhesion improver a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.
- the type of silane coupling agent various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more.
- Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
- 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 are effective in terms of coatability.
- surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), KP340.
- 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.
- Pigment derivative The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
- a pigment derivative as a dispersion aid
- As pigment derivatives azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine
- derivatives such as phthalocyanines and quinophthalones are preferable.
- Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton.
- 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.
- a 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 photoacid generator 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 62 , R 63 , R 64 , R 65 , R 66 and R 67 represent a —CH 2 OR 68 group
- R 61 is an aryl group having 6 to 12 carbon atoms
- one of R 62 , R 63 , R 64 and R 65 is —CH 2 OR
- R 68 represents a hydrogen atom or 1 to 4 represents an alkyl group.
- 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 use 2 or more types together.
- the amount when the crosslinking agent is used is preferably from 0.1 to 15% by mass, particularly preferably from 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 photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control. It is considered that the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled because it contains a polymerization inhibitor and inhibits radical polymerization of the lower layer of the coating film.
- the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, 2,6-di-tert-butyl-4-cresol is preferable from the viewpoint of shape control.
- a polymerization inhibitor contains 1 type (s) or 2 or more types.
- a polymerization inhibitor may be contained in the resin, and it may be used as the polymerization inhibitor of the present invention. In addition to the polymerization inhibitor in the resin, The same or different polymerization inhibitor may be added during the production of the photosensitive coloring composition.
- the content ratio is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, in the total solid content of the photosensitive coloring composition, More preferably, it is 0.01 mass% or more, and is 0.3 mass% or less normally, Preferably it is 0.2 mass% or less, More preferably, it is 0.1 mass% or less.
- the combination of the upper limit and the lower limit is preferably 0.0005 to 0.3% by mass, more preferably 0.001 to 0.2% by mass, and further preferably 0.01 to 0.1% by mass.
- the content ratio of the colorant (a) is not particularly limited, but is usually 10% by mass or more and 20% by mass or more in the total solid content in the photosensitive coloring composition. More preferably, it is more preferably 25% by mass or more, even more preferably 30% by mass or more, particularly preferably 32% by mass or more, most preferably 35% by mass or more, Further, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, still more preferably 40% by mass or less, and 38% by mass or less. It is particularly preferable that it is 35% by mass or less.
- the combination of the upper limit and the lower limit is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, next more preferably 25 to 45% by mass, further preferably 30 to 40% by mass, and more preferably 32 to 38% by mass. % Is more preferable, and 35 to 38% by mass is particularly preferable.
- the content ratio of the (a1) organic black pigment is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass in the total solid content of the photosensitive coloring composition. More preferably, it is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and 20% by mass or less. Particularly preferred.
- the amount is not less than the lower limit, sufficient light shielding properties tend to be obtained, and when the amount is not more than the upper limit, electric reliability tends to be increased.
- the combination of the upper limit and the lower limit is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, further preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass.
- the content ratio of Pigment Blue 60 is not particularly limited, but is preferably 2% by mass or more, more preferably 3% by mass or more, and more preferably 4% by mass or more in the total solid content of the photosensitive coloring composition. Is more preferably 6% by mass or more, particularly preferably 8% by mass or more, and most preferably 10% by mass or more. Further, it is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, still more preferably 9% by mass or less, and 8% by mass or less.
- the transmittance near 700 nm tends to decrease, and when it is at most the upper limit value, electrical reliability tends to be high and sufficient plate-making characteristics tend to be obtained.
- the combination of the upper limit and the lower limit is preferably 2 to 15% by mass, more preferably 3 to 15% by mass, further preferably 4 to 12% by mass, and particularly preferably 6 to 12% by mass.
- the content ratio of the carbon black content is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the photosensitive coloring composition. It is more preferably at least 4% by mass, particularly preferably at least 4% by mass, more preferably at most 10% by mass, more preferably at most 9% by mass, and at most 8% by mass. Is more preferably 7% by mass or less, and particularly preferably 5% by mass or less. When the amount is not less than the lower limit, sufficient light shielding properties tend to be obtained. When the amount is not more than the upper limit, the transmittance in the near infrared region tends to increase.
- the combination of the upper limit and the lower limit is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, further preferably 3 to 8% by mass, still more preferably 4 to 7% by mass, and 4 to 5% by mass. % Is particularly preferable.
- the content ratio is not particularly limited, but is preferably 1% by mass or more and more preferably 2% by mass or more in the total solid content of the photosensitive coloring composition.
- 3% by mass or more is more preferable, 4% by mass or more is more preferable, 6% by mass or more is particularly preferable, 7% by mass or more is most preferable, 15% by mass or less is preferable, and 12% by mass or less is more preferable.
- 10 mass% or less is more preferable, and 8 mass% or less is especially preferable.
- the combination of the upper limit and the lower limit is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, further preferably 3 to 10% by mass, still more preferably 4 to 8% by mass, and 6 to 8% by mass. % Is particularly preferable, and 7 to 8% by mass is most preferable.
- the content ratio of the (a1) organic black pigment to the total colorant contained in the photosensitive coloring composition is not particularly limited, but is preferably 20% by mass or more, and 30% by mass or more. More preferably, it is more preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 60% by mass or more, and 80% by mass or less. It is preferably 75% by mass or less, more preferably 70% by mass or less, and particularly preferably 65% by mass or less.
- the combination of the upper limit and the lower limit is preferably 20 to 80% by mass, more preferably 30 to 80% by mass, more preferably 40 to 75% by mass, and further preferably 50 to 70% by mass.
- the content ratio of Pigment Blue 60 is not particularly limited, but is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, and 18% by mass or more. Is more preferably 20% by mass or more, still more preferably 24% by mass or more, particularly preferably 28% by mass or more, and is also 50% by mass or less. It is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less.
- the transmittance near 700 nm tends to decrease, and when it is at most the upper limit value, electrical reliability tends to be high and sufficient plate-making characteristics tend to be obtained.
- the combination of the upper limit and the lower limit is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, further preferably 18 to 40% by mass, still more preferably 24 to 35% by mass, and 28 to 35% by mass. % Is particularly preferable.
- the content ratio of (a3) carbon black to (a) the colorant contained in the photosensitive coloring composition is not particularly limited, but is preferably 10% by mass or more, and 12% by mass or more. More preferably, it is more preferably 15% by mass or more, more preferably 18% by mass or more, particularly preferably 20% by mass or more, and preferably 35% by mass or less, and 30% by mass or less. More preferably, it is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
- the combination of the upper limit and the lower limit is preferably 10 to 35% by mass, more preferably 12 to 30% by mass, further preferably 15 to 25% by mass, and particularly preferably 18 to 20% by mass.
- (a3) In addition to carbon black, (a1) Including a predetermined amount of an organic black pigment, after securing a transmittance in the vicinity of a wavelength of 900 nm It is considered that sufficient light shielding properties can be secured.
- the content ratio of (a1) organic black pigment to 100 parts by mass of carbon black is usually 150 parts by mass or more, preferably 180 parts by mass or more, more preferably 200 parts by mass or more, and 210 parts by mass.
- it is at least 220 parts by weight, more preferably at least 220 parts by weight, even more preferably at least 250 parts by weight, even more preferably at least 300 parts by weight, and at least 350 parts by weight. More preferably, it is more preferably 400 parts by mass or more, still more preferably 450 parts by mass or more, and most preferably 480 parts by mass or more. Further, it is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, still more preferably 600 parts by mass or less, and particularly preferably 500 parts by mass or less. When it is at least the lower limit value, the transmittance in the near-infrared region tends to be high, and when it is at most the upper limit value, the electrical reliability tends to be high.
- the combination of the upper limit and the lower limit is preferably 150 to 1000 parts by mass, more preferably 180 to 800 parts by mass, next preferably 200 to 800 parts by mass, further preferably 210 to 600 parts by mass, and 220 to 600 parts by mass.
- 450 to 500 parts by mass is particularly preferable, and 480 to 500 parts by mass is most preferable.
- the content ratio of the total organic pigment to 100 parts by mass of carbon black is usually preferably 300 parts by mass or more, preferably 400 parts by mass or more, more preferably 500 parts by mass or more, further preferably 550 parts by mass or more, and 600 parts by mass or more. Is more preferable, 620 parts by mass or more is particularly preferable, 650 parts by mass or more is most preferable, 900 parts by mass or less is preferable, and 800 parts by mass or less is more preferable.
- the transmittance near the wavelength of 900 nm tends to be high, and by setting the upper limit value or less, sufficient light shielding properties can be obtained, and light leakage near the wavelength of 700 nm can be suppressed.
- the combination of the upper limit and the lower limit is preferably 300 to 900 parts by mass, more preferably 400 to 900 parts by mass, next more preferably 500 to 900 parts by mass, further preferably 550 to 800 parts by mass, and 600 to 800 parts by mass. Is more preferable, 620 to 800 parts by mass is particularly preferable, and 650 to 800 parts by mass is most preferable.
- the content ratio of Pigment Blue 60 is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, further preferably 150 parts by mass or more, still more preferably 180 parts by mass or more, and particularly preferably 200 parts by mass or more. More preferably, it is more preferably not less than 220 parts by mass, most preferably not less than 240 parts by mass, more preferably not more than 400 parts by mass, and even more preferably not more than 300 parts by mass.
- the combination of the upper limit and the lower limit is preferably 50 to 400 parts by mass, more preferably 100 to 400 parts by mass, further preferably 150 to 400 parts by mass, still more preferably 200 to 300 parts by mass, and 220 to 300 parts by mass. Part is particularly preferred, with 240 to 300 parts by weight being most preferred.
- the content ratio of the purple pigment with respect to 100 parts by mass of the organic black pigment is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 40 parts by mass or more, and even more preferably 55 parts by mass or more. It is particularly preferably at least 65 parts by mass, particularly preferably at least 65 parts by mass, most preferably at least 70 parts by mass, more preferably at most 100 parts by mass, more preferably at most 90 parts by mass, further preferably at most 80 parts by mass. More preferably, it is more preferably 65 parts by mass or less.
- the combination of the upper limit and the lower limit is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass, next preferably 40 to 100 parts by mass, further preferably 55 to 100 parts by mass, and 60 to 100 parts by mass. Is more preferably 65 to 90 parts by weight, and most preferably 70 to 90 parts by weight.
- the content rate of alkali-soluble resin is not specifically limited, It is 5 mass% or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 30% by mass or more, particularly preferably 35% by mass or more, and is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and still more preferably. Is 50% by mass or less, particularly preferably 45% by mass or less.
- the combination of the upper limit and the lower limit is, for example, preferably 10 to 85% by mass, more preferably 20 to 80% by mass, next preferably 30 to 70% by mass, further preferably 35 to 60% by mass, 60% by mass is even more preferable, and 40 to 50% by mass is particularly preferable.
- the content ratio of the (b1) epoxy (meth) acrylate resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% in the total solid content of the photosensitive coloring composition of the present invention. It is at least mass%, more preferably at least 20 mass%, particularly preferably at least 25 mass%, usually at most 45 mass%, preferably at most 40 mass%, more preferably at most 35 mass%.
- the combination of the upper limit and the lower limit is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, further preferably 15 to 40% by mass, still more preferably 20 to 35% by mass, and 25 to 35% by mass. % Is particularly preferable.
- the content of the (b1) epoxy (meth) acrylate resin contained in the alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more. Yes, usually 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less.
- the combination of the upper limit and the lower limit is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and further preferably 40 to 80% by mass.
- the content rate of a photoinitiator is not specifically limited, It is 0.1 mass% or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 0.5 mass% or more, More preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, particularly preferably 4% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass. % Or less, more preferably 7% by mass or less.
- the combination of the upper limit and the lower limit is preferably from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, further preferably from 1 to 8% by mass, still more preferably from 2 to 8% by mass, 3 to 8% by mass is particularly preferable, and 4 to 7% by mass is most preferable.
- the content ratio of the polymerization accelerator is not particularly limited, but preferably 0.05% by mass or more in the total solid content of the photosensitive coloring composition of the present invention. It is usually 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 (c) photopolymerization initiator. It is preferable to use in the ratio.
- the content ratio of the polymerization accelerator By setting the content ratio of the polymerization accelerator to the lower limit value or more, there is a tendency to suppress the decrease in sensitivity to the exposure light beam, and by setting the content ratio to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer is suppressed. However, there is a tendency that development defects can be suppressed.
- the content rate is not specifically limited, However, From a viewpoint of sensitivity, It is normally 20 mass% or less in the total solid in a photosensitive coloring composition, Preferably It is 15 mass% or less, More preferably, it is 10 mass% or less.
- the content rate of an ethylenically unsaturated compound is not specifically limited, It is 1 mass% or more normally in the total solid of the photosensitive coloring composition of this invention, Preferably it is 5 mass% or more, More preferably, it is 10 mass%. In addition, it is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less. It is possible to maintain appropriate sensitivity by setting it to the lower limit value or more, to suppress dissolution of the exposed portion by the developer, and to suppress deterioration of sharpness and adhesion of the pixel, and below the upper limit value. By doing so, it tends to be easy to suppress the increase in the permeability of the developing solution to the exposed portion and obtain a good image.
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and further preferably 10 to 15% by mass.
- the photosensitive coloring composition of this invention is 5 mass% or more normally by using a (e) solvent, Preferably it is 10 mass% or more, Preferably it is 10 mass% or more, More preferably, 15 mass% or more, Further, it is usually prepared so as to be 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.
- the combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.
- the content rate of a dispersing agent is not specifically limited, It is 1 mass% or more normally in the total solid of a photosensitive coloring composition, 3 mass% or more is preferable, 5 mass% or more is more preferable, and usually 30 mass% or less and 20 mass% or less are preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable.
- the amount is not less than the lower limit value, sufficient dispersibility tends to be obtained, and when the amount is not more than the upper limit value, the ratio of other components is relatively reduced, so that sensitivity, plate-making property, and the like are lowered. There is a tendency to be able to suppress.
- the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, further preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
- the content ratio of the (f) dispersant to (a) 100 parts by mass of the colorant is usually preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and usually 50 parts by mass or less. It is preferable that it is 30 mass parts or less.
- the amount is not less than the lower limit value, sufficient dispersibility tends to be obtained, and when the amount is not more than the upper limit value, the ratio of other components is relatively reduced, so that sensitivity, plate-making property, and the like are lowered. There is a tendency to be able to suppress.
- the combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and further preferably 15 to 30 parts by mass.
- the content ratio of (b) alkali-soluble resin to 100 parts by mass of (d) ethylenically unsaturated compound is usually preferably 80 parts by mass or more, more preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and 200 parts by mass.
- the above is more preferable, 250 parts by mass or more is particularly preferable, usually 700 parts by mass or less, 500 parts by mass or less is preferable, 400 parts by mass or less is more preferable, and 300 parts by mass or less is more preferable.
- the combination of the upper limit and the lower limit is, for example, preferably 80 to 700 parts by weight, more preferably 100 to 500 parts by weight, further preferably 150 to 400 parts by weight, particularly preferably 200 to 300 parts by weight, and 250 to 300 parts by weight. Part by mass is most preferred.
- the content is not particularly limited, but is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0% in the total solid content of the photosensitive coloring composition. 4 to 2% by mass.
- the effect of improving the adhesion can be sufficiently obtained by setting the content ratio of the adhesion improver to the above lower limit value or more, and the sensitivity is lowered by setting it to the upper limit value or less, or a residue remains after development. There exists a tendency which can suppress becoming a defect.
- the content is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably in the total solid content of the photosensitive coloring composition. Is from 0.01 to 0.5% by weight, most preferably from 0.03 to 0.3% by weight.
- the smoothness and uniformity of the coating film tends to be manifested by setting the content ratio of the surfactant to the lower limit value or more, and the smoothness and uniformity of the coating film is manifested by setting the content ratio to the upper limit value or less. It tends to be easy to suppress deterioration of other characteristics.
- the photosensitive coloring composition of the present invention can be suitably used for forming a colored spacer, and is preferably black from the viewpoint of being used as a colored spacer.
- the optical density (OD) per 1 ⁇ m of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.3 or more. Is more preferably 4 or more, particularly preferably 1.5 or more, most preferably 1.8 or more, usually 4.0 or less, and preferably 3.0 or less. More preferably, it is 2.5 or less.
- the combination of the upper limit and the lower limit is preferably 1.0 to 4.0, more preferably 1.2 to 3.0, further preferably 1.3 to 3.0, and 1.4 to 3.0. Even more preferred is 1.5 to 3.0, and most preferred is 1.8 to 2.5.
- the transmittance at a wavelength of 700 nm is preferably 2.5% or less, more preferably 2.0% or less, further preferably 1.5% or less, and usually 0 .01% or more.
- the combination of the upper limit and the lower limit is preferably 0.01 to 2.5%, more preferably 0.01 to 2.0%, and still more preferably 0.01 to 1.5%.
- the light-sensitive coloring composition of the present invention preferably has a transmittance at a wavelength of 900 nm of 10% or more, more preferably 15% or more, further preferably 20% or more, and usually 100% or less.
- the combination of the upper limit and the lower limit is preferably 10 to 100%, more preferably 15 to 100%, and further preferably 20 to 100%.
- the colored spacer may be formed on the array substrate (TFT side substrate). In this case, it is necessary to form the colored spacer in accordance with the position of the TFT pattern on the substrate.
- As a method of forming a colored spacer at a predetermined position it is possible to read a mark on the array substrate with light having a wavelength of about 900 nm and perform alignment of the photomask. When the alignment is performed, the mark is colored.
- the transmittance of the coating film at a wavelength of 900 nm is a predetermined value or more. Therefore, by setting the transmittance at a wavelength of 900 nm or more to the lower limit value or more, the visibility of the mark is improved, and a colored spacer tends to be easily formed at a predetermined position.
- the transmittance of the photosensitive coloring composition at a wavelength of 700 nm or 900 nm is obtained by forming a cured film having a film thickness of 2.5 ⁇ m using the photosensitive coloring composition and measuring the transmittance at a wavelength of 700 nm or 900 nm with a spectrophotometer.
- a spectrophotometer Just measure. Although detailed measurement conditions etc. are not specifically limited, For example, it can measure by the method as described in the Example mentioned later.
- the photosensitive coloring composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
- the colorant is preferably dispersed 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 part or all of (a) a colorant, (e) a solvent, (f) a dispersant, and (b) an alkali-soluble resin are used together (hereinafter referred to as dispersion).
- the mixture subjected to the treatment and the composition obtained by the treatment may be referred to as “ink” or “pigment dispersion”).
- a polymer dispersant as the dispersant (f) because the resulting ink and resist are prevented from thickening with time (excellent in dispersion stability).
- a colorant, (e) organic solvent, and (f) dispersant that can be used in the pigment dispersion those described as those that can be used in the photosensitive coloring composition are preferably employed. Can do.
- a content rate in a photosensitive coloring composition can also be preferably employ
- a dispersion treatment when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring 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.
- the colorant is dispersed with a sand grinder, glass beads or zirconia beads having a particle 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 may be mixed in the liquid. Therefore, the obtained resist is preferably filtered by a filter or the like.
- a cured product can be obtained by curing the photosensitive coloring composition of the present invention.
- a cured product obtained by curing the photosensitive coloring composition can be suitably used as a colored spacer.
- the material thereof is not particularly limited.
- Transparent substrates are mainly used.
- materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, sheets made of thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy.
- thermosetting resin sheets such as resins, unsaturated polyester resins, poly (meth) acrylic resins, and various glasses.
- 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 colored composition of the present invention is used for the same applications as known photosensitive colored compositions for color filters. Hereinafter, it is used as a colored spacer (black photospacer). The method for forming a black photospacer using the photosensitive coloring composition of the present invention will be described below.
- a photosensitive coloring composition is supplied in a film shape or a pattern shape by a method such as coating on a substrate on which a black photospacer is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as exposure-development photolithography. Thereafter, a black photo spacer is formed on the substrate by performing additional exposure or thermosetting treatment as necessary.
- the photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent.
- a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Further, it may be supplied in a pattern by an inkjet method or a printing method. Above all, the die coating method reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. It is preferable from the viewpoint.
- the coating amount varies depending on the application, but in the case of a black photospacer, for example, the dry film thickness is usually in the range of 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, particularly preferably 1 ⁇ m to 7 ⁇ m.
- the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel.
- the final height of the black photo spacers is different.
- a known substrate such as a glass substrate can be used as the substrate.
- the substrate surface is preferably a flat surface.
- Drying method Drying after supplying the photosensitive coloring composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a reduced pressure chamber, without raising temperature.
- Drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used.
- the drying time is usually selected within a range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component and the performance of the dryer used.
- the temperature is selected in the range of 30 seconds to 3 minutes.
- Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating with an ultraviolet light source or a visible light source through this mask pattern.
- the exposure mask is placed close to the coating film of the photosensitive coloring composition, or the exposure mask is arranged at a position away from the coating film of the photosensitive coloring composition.
- a method of projecting exposure light through a mask may be used. Further, a scanning exposure method using a laser beam without using a mask pattern may be used.
- the exposure is performed in a deoxygenated atmosphere or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.
- a light shielding portion (light transmittance 0%) and a plurality of openings have the highest average light transmittance.
- An exposure mask having an opening (intermediate transmission opening) having a small average light transmittance with respect to a high opening (complete transmission opening) is used.
- a difference in the residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the complete transmission opening, that is, a difference in exposure amount.
- a method of creating the intermediate transmission opening by a matrix-shaped light shielding pattern having a minute polygonal light shielding unit is known.
- a method of controlling the light transmittance with a film of a material such as chromium, molybdenum, tungsten, or silicon as the absorber.
- the light source used for the above exposure is not particularly limited.
- the light source for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser,
- laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser.
- An optical filter can also be used when used by irradiating light of a specific wavelength.
- the optical filter may be of a type that can control the light transmittance at the exposure wavelength with a thin film, for example, and the material in that case is, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.), Examples include MoSi, Si, W, and Al.
- a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
- Energy of exposure generally, 1 mJ / cm 2 or more, preferably 5 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, usually 300 mJ / cm 2 or less, preferably 200 mJ / cm 2 or less, more preferably 150 mJ / cm 2 or less.
- the distance between the exposure target and the mask pattern is usually 10 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and usually 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 300 ⁇ m or less.
- an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
- This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
- Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate
- Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
- Organic alkaline compounds. These alkaline compounds may be a mixture of two or more.
- surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids.
- nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters
- Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfon
- organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like.
- the organic solvent 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 may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment.
- the thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 ° C. to 280 ° C., preferably in the range of 150 ° C. to 250 ° C., and the time is selected in the range of 5 minutes to 60 minutes.
- the size and shape of the colored spacer of the present invention are appropriately adjusted depending on the specifications of the color filter to which the colored spacer is applied, but the photosensitive colored composition of the present invention is particularly suitable for the height of the spacer and the sub-spacer by photolithography. It is useful for simultaneously forming different black photo spacers, in which case the height of the spacer is usually about 2 to 7 ⁇ m, and the sub-spacer is usually about 0.2 to 1.5 ⁇ m lower than the spacer.
- the optical density (OD) per 1 ⁇ m of the colored spacer of the present invention is preferably 1.2 or more, more preferably 1.5 or more, further preferably 1.8 or more, from the viewpoint of light-shielding properties.
- the optical density (OD) is a value measured by a method described later.
- the combination of the upper limit and the lower limit is preferably 1.2 to 4.0, more preferably 1.5 to 3.0, and even more preferably 1.8 to 3.0.
- the color filter can form red, green, and blue pixel coloring layers on a liquid crystal driving substrate (array substrate). Or you may form a pixel coloring layer on the glass substrate as a transparent substrate.
- the image display apparatus of the present invention includes the above-described colored spacer of the present invention.
- an alignment film is formed on a liquid crystal driving substrate (array substrate) having the colored spacer of the present invention, a liquid crystal cell is formed by bonding to a counter electrode substrate, and liquid crystal is injected into the formed liquid crystal cell.
- an image display device such as a liquid crystal display device provided with the colored spacer.
- the colored spacer of the present invention can also be formed by placing the colored spacer of the present invention on the counter electrode substrate side, bonding the liquid crystal driving substrate (array substrate) to form a liquid crystal cell, and injecting the liquid crystal into the formed liquid crystal cell.
- An image display device such as a liquid crystal display device can be manufactured. Further, for example, as described in JP-A-2014-215614, liquid crystal alignment can be improved by using a specific alignment material and injecting liquid crystal into a liquid crystal cell and then irradiating ultraviolet rays.
- 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.
- Block copolymer, amine value is 70 mgKOH / g
- acid value is 1 mgKOH / g or less.
- the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).
- the content of the repeating units of the following formulas (1a), (2a), and (3a) in all the repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.
- DPHA Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate ⁇ additive> “KAYAMER PM-21” (phosphate containing methacryloyl group) manufactured by Nippon Kayaku Co., Ltd. ⁇ Surfactant> Made by DIC "Megafuck F-559"
- Pigment dispersion 3 ⁇ Preparation of pigment dispersion 3> Pigment dispersion, except that the pigment, dispersant, dispersion aid, alkali-soluble resin, and solvent described in Table 1 were mixed so as to have the mass ratio described in Table 1 and the dispersion treatment time was changed to 6 hours. Dispersion was carried out in the same manner as in liquids 1, 2, 4, 5 and 6, and pigment dispersion 3 was prepared.
- Examples 1 to 12 and Comparative Examples 1 to 5 Using the pigment dispersions 1 to 6 prepared above, other components were added so that the ratio in the solid content was the mixing ratio shown in Tables 2 to 5, and the total solid content was 19% by mass. Thus, PGMEA was added, stirred and dissolved to prepare a photosensitive coloring composition and evaluated by the following method.
- each photosensitive coloring composition prepared was applied to a glass substrate with a spin coater so that the film thickness after post-baking was 2.5 ⁇ m, dried under reduced pressure for 1 minute, and then heated at 90 ° C. with a hot plate at 90 ° C. Dry for 2 seconds. Thereafter, the entire surface was exposed under the exposure conditions of 400 mJ / cm 2 and illuminance of 45 mW / cm 2 using a high-pressure mercury lamp, and heated (230 ° C.) for 20 minutes to obtain a resist-coated substrate.
- the optical density (OD value) 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.
- the optical density (unit OD value) per unit film thickness (1 ⁇ m) was calculated from the optical density (OD value) and film thickness.
- the OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.
- transmittance at wavelengths of 700 nm and 900 nm was measured with a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation).
- a glass substrate not coated with the photosensitive coloring composition was used as a reference.
- the transmittance at a wavelength of 700 nm is an indicator of light leakage, and the smaller the value, the better. If it is 2.5% or less, there exists a preferable tendency.
- the transmittance at a wavelength of 900 nm is an index of mark readability for mask alignment, and the larger the value, the better. If it is 10% or more, there exists a preferable tendency.
- Tables 2 to 5 show the measurement results of unit OD value and transmittance.
- VHR voltage holding ratio
- ion density ⁇ Evaluation of voltage holding ratio (VHR) and ion density> The voltage holding ratio (VHR) and ion density were evaluated by the methods described below.
- FIG. 1 is a schematic view of the upper surface of the electrode substrate B (20).
- Each photosensitive coloring composition was apply
- the electrode substrate A on which the coating film was formed was post-baked at 230 ° C. for 20 minutes to obtain an electrode substrate (resist substrate) on which the colored cured film (3) was formed. Thereafter, a polyimide solution was applied to the resist substrate, pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes. The resist substrate thus obtained was cut into a 2.5 cm square substrate to complete an evaluation electrode substrate A (8).
- a polyimide solution is applied also onto the electrode substrate B (20), pre-baked on a hot plate at 70 ° C. for 2 minutes, and post-baked at 220 ° C. for 24 minutes, and the evaluation electrode substrate B (9) Was completed.
- an epoxy resin-based sealant (5) containing silica beads having a diameter of 5 ⁇ m is applied on the outer periphery of the evaluation electrode substrate B (9) using a dispenser, and then the evaluation electrode substrate B (9)
- An empty cell was created by pasting the coated surface of the electrode substrate A (8) for evaluation on the front side (sealant side) while being crimped. The created empty cell was heated in a hot air circulating furnace at 180 ° C. for 2 hours.
- Liquid crystal (7) (MLC-6608 manufactured by Merck Japan Ltd.) was injected into the empty cell thus obtained, and the peripheral part was sealed with a UV curable sealant (6).
- the liquid crystal cell was annealed (heated in a hot-air circulating furnace at 105 ° C. for 2.5 hours), and then irradiated with ultraviolet light at a pressure of 18 J / cm 2 and an illuminance of 40 mW / cm 2 with a high-pressure mercury lamp. ) Completed.
- the colored cured film is 1.7 cm square, and the electrode portion is 1 cm square.
- FIG. 2 shows a schematic side view of the completed measurement liquid crystal cell (30).
- VHR voltage holding ratio
- the ion density can be measured by the method described in, for example, International Display Workshop (IDW) '06 Proceedings LCT7-1.
- IDT International Display Workshop
- a voltage is gradually applied, so that the ion peak and the liquid crystal alignment peak can be distinguished and measured, and there may be a case where a difference in reliability that is difficult to make a difference in voltage holding ratio can be measured.
- Impurity ions may cause display defects such as afterimages and flickers in a liquid crystal display device, and ion density measurement is effective for the evaluation.
- FIG. 3 shows a schematic diagram of the applied voltage value (11), the measured current value (12), and the impurity ion peak portion (13) when the time of one cycle is taken on the horizontal axis. The measurement results are shown in Tables 2, 4 and 5.
- the photosensitive coloring compositions of Examples 1 to 4 and Comparative Examples 1 to 4 in Table 2 all have the same unit OD value of the coated substrate, that is, have the same light shielding properties.
- the coated substrate using the active coloring composition has a sufficiently low transmittance at a wavelength of 700 nm and an excellent light-shielding property for visible light in a long wavelength region, and has a sufficiently high transmittance at a wavelength of 900 nm so that marks can be read for mask alignment. Was confirmed to be good.
- the voltage holding ratio at 2.0 Hz after ultraviolet irradiation is high, it was confirmed that liquid crystal driving is not hindered even when a panel forming method in which ultraviolet irradiation is performed after forming a liquid crystal cell is adopted.
- the coated substrate using the photosensitive coloring composition of Comparative Example 1 had a low transmittance at a wavelength of 900 nm, and the mark readability for mask alignment was insufficient.
- the coated substrate using the photosensitive coloring composition of Comparative Examples 2 and 3 has a high transmittance at a wavelength of 700 nm, has insufficient light-shielding property for visible light in a long wavelength region, and light leakage has occurred. It was done.
- the coating substrate using the photosensitive coloring composition of the comparative example 2 was confirmed to inhibit liquid crystal driving.
- the coated substrate using the photosensitive coloring composition of Comparative Example 4 had no problem with the transmittance at a wavelength of 900 nm and the transmittance at a wavelength of 700 nm, but had a low voltage holding ratio at 2.0 Hz after ultraviolet irradiation. From this, it was confirmed that the liquid crystal driving was hindered.
- carbon black can absorb light at a wavelength of 700 nm sufficiently because carbon black has a high absorbance in the entire wavelength range of visible light.
- the absorbance in the infrared region is high and the transmittance in the region is low, as in Comparative Example 1, when (a3) the content ratio of the organic black pigment is low with respect to 100 parts by mass of carbon black, that is, the black pigment When the proportion of (a3) carbon black is high, the transmittance at a wavelength of 900 nm is low.
- a specific organic black pigment, a blue pigment and carbon black are used in combination, and the ratio of the specific organic black pigment to carbon black is made appropriate.
- the transmittance at a wavelength of 900 nm is sufficiently high, the readability of a mark for mask alignment is sufficient, and the transmittance at a wavelength of 700 nm is sufficiently low, so that light leakage can be prevented.
- C.I. By selecting I. Pigment Blue 60, the voltage holding ratio at 2.0 Hz after ultraviolet irradiation is high, and the electrical reliability can be increased.
- the photosensitive coloring compositions of Example 1 and Comparative Example 5 in Table 5 have the same composition except that the types of organic black pigments are different, but the photosensitive coloring composition of Example 1 is after UV irradiation. Therefore, it was confirmed that the electrical reliability was good. From this, it became clear that electrical reliability can be improved by using (a1) organic black pigment as the organic black pigment.
- the photosensitive coloring composition of the present invention it is possible to provide a cured product and a colored spacer that have little light leakage around a wavelength of 700 nm, excellent transmittance near a wavelength of 900 m, and excellent electrical reliability after ultraviolet irradiation. Furthermore, an image display apparatus provided with such a colored spacer can be provided. Therefore, the present invention has very high industrial applicability in the fields of photosensitive coloring composition, cured product, coloring spacer and image display device.
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Abstract
Description
2017年2月15日に日本国特許庁に出願された日本国特願2017-026369、及び2017年8月31日に日本国特許庁に出願された日本国特願2017-166318の明細書、特許請求の範囲、図面及び要約書の全内容、並びに、本明細書で引用された文献等に開示された内容の一部又は全部をここに引用し、本明細書の開示内容として取り入れる。
一方で、液晶配向性向上のため液晶セル作成後に紫外線照射を行う方法が広がってきている。紫外線照射を行うと顔料あるいはその処理剤等の一部が分解し、不純物を生じる傾向があるが、その場合においても十分な電気信頼性を保つことが要求されている。
また特許文献2に記載されている感光性着色組成物について検討したところ、特に紫外線照射後に電気信頼性を確保することが困難であった。
すなわち、本発明は以下の[1]~[12]の構成を有する。
前記(a)着色剤が、(a1)下記一般式(I)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料、(a2)C.I.ピグメントブルー60、並びに(a3)カーボンブラックを含み、
前記(a3)カーボンブラック100質量部に対する前記(a1)有機黒色顔料の含有割合が150質量部以上であることを特徴とする感光性着色組成物。
R2、R3、R4、R5、R7、R8、R9及びR10は各々独立に水素原子、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又はSO2NR11R12であり;
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、互いに直接結合することもでき、又は酸素原子、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;
R11及びR12は各々独立に、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又は炭素数2~12のアルキニル基である。)
[3]前記(a3)カーボンブラック100質量部に対する前記(a1)有機黒色顔料の含有割合が210質量部以上である、[1]又は[2]に記載の感光性着色組成物。
[4]前記(a3)カーボンブラック100質量部に対する前記(a2)C.I.ピグメントブルー60の含有割合が200質量部以上である、[1]~[3]のいずれか1項に記載の感光性着色組成物。
[5]前記(a3)カーボンブラック100質量部に対する全有機顔料の含有割合の合計が550質量部以上である、[1]~[4]のいずれか1項に記載の感光性着色組成物。
[6]前記(a)着色剤の含有割合が全固形分中10質量%以上である、[1]~[5]のいずれか1項に記載の感光性着色組成物。
[7]前記(a)着色剤の含有割合が全固形分中45質量%以下である、[1]~[6]のいずれか1項に記載の感光性着色組成物。
[8]前記(b)アルカリ可溶性樹脂が、(b1)エポキシ(メタ)アクリレート系樹脂を含有する、[1]~[7]のいずれか1項に記載の感光性着色組成物。
[9]硬化した塗膜の膜厚1μm当たりの光学濃度が1.0以上である、[1]~[8]のいずれか1項に記載の感光性着色組成物。
[11][10]に記載の硬化物から形成される着色スペーサー。
[12][11]に記載の着色スペーサーを備える画像表示装置。
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。
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。
本発明の感光性着色組成物は、
(a)着色剤
(b)アルカリ可溶性樹脂
(c)光重合開始剤
(d)エチレン性不飽和化合物
(e)溶剤
(f)分散剤を必須成分として含有し、必要に応じて、更に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、溶剤に溶解又は分散した状態で使用される。
本発明の感光性着色組成物における(a)着色剤は、下記(a1)、(a2)及び(a3)を必須成分として含有する。
(a1)後述の一般式(I)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料
(a2)C.I.ピグメントブルー60
(a3)カーボンブラック
これらの顔料うち、(a1)及び(a2)は有機顔料であり、(a3)は無機顔料である。
前述のとおり、本発明の感光性着色組成物に含まれる(a)着色剤は、(a1)下記一般式(I)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料(以下、「(a1)有機黒色顔料」と略記する場合がある。)を必須成分として含有する。(a1)有機黒色顔料を含有することにより、遮光性を確保し、液晶の電圧保持率の低下を抑制し、また、紫外線の吸収を抑制して形状や段差をコントロールしやすくできると考えられる。
R2、R3、R4、R5、R7、R8、R9及びR10は各々独立に水素原子、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又はSO2NR11R12であり;
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、互いに直接結合することもでき、又は酸素原子、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;
R11及びR12は各々独立に、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又は炭素数2~12のアルキニル基である。
R3及びR8は各々独立に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又はSO3 -であり、さらに好ましくは水素原子又はSO3Hである。
好ましくは、R1とR6、R2とR7、R3とR8、R4とR9、及び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の置換基で構成され、より好ましくは、R1はR6と同一の置換基であり、R2はR7と同一の置換基であり、R3はR8と同一の置換基であり、R4はR9と同一の置換基であり、かつ、R5はR10と同一の置換基である。
この有機黒色顔料は、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(I)で表される化合物のスルホン酸誘導体(スルホン酸置換体)、特に前記一般式(I-1)で表される化合物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ため、前記(a1)有機黒色顔料がこれらのスルホン酸誘導体をさらに含むことが好ましい。スルホン酸誘導体としては、例えば、前記一般式(I)において、R2、R3、R4、R5、R7、R8、R9及びR10からなる群から選ばれる少なくとも1つがSO3Hのものが挙げられる。
また、色度調整のために、前記(a1)有機黒色顔料がさらに下記一般式(I-2)で表される化合物及び/又は前記化合物の幾何異性体を含むことが好ましい。
本発明の感光性着色組成物に含まれる(a)着色剤は、(a2)C.I.ピグメントブルー60を必須成分として含有する。
前記(a1)有機黒色顔料は波長650~750nm付近の透過率が高く、該波長領域の遮光性が不十分であるが、(a2)C.I.ピグメントブルー60は該波長領域に吸収帯を有しているため、(a2)C.I.ピグメントブルー60を併用することで該波長領域における透過率を低下できるものと考えられる。
本発明の感光性着色組成物に含まれる(a)着色剤は、(a3)カーボンブラックを必須成分として含有する。
(a3)カーボンブラックは可視領域の全波長において全面的に吸収スペクトルを有し、かつ、透過率も低いため、(a1)有機黒色顔料、(a2)C.I.ピグメントブルー60に加えて(a3)カーボンブラックを含有することで、高遮光性を達成することができるとともに、光漏れも抑制でき、また、全固形分に対する着色剤の含有割合を低くでき、それによって高い電気信頼性を確保できるものと考えられる。
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、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、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
ビルラー社製: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
なお、カーボンブラックの表面のpHは、カーボンブラックの粉体を水に分散させ、該分散液につき水系のpH測定を行うことにより測定される。
本発明におけるカーボンブラックの平均粒子径は数平均粒子径を意味する。一般的にカーボンブラックの平均粒子径は電子顕微鏡観察により数万倍で撮影された写真を数視野撮影し、これらの写真の粒子を画像処理装置により2000~3000個程度計測する粒子画像解析により求められる。
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。被覆樹脂の量は、カーボンブラックと樹脂の合計量に対し1~30質量%が好ましい。前記下限値以上とすることで被覆を十分なものとすることができる傾向がある。一方、前記上限値以下とすることで、樹脂同士の粘着を防ぎ、分散性が良好なものとすることができる傾向がある。
本発明の感光性着色組成物に含まれる(a)着色剤は、上記(a1)、(a2)及び(a3)の顔料以外に、その他の顔料やその他の染料等のその他の着色剤を含んでいてもよい。その他の着色剤の色には特に制限はなく、赤、橙、青、紫、緑、黄色等の各色の着色剤を用いることができる。また、上記(a1)及び(a3)以外の黒色顔料を用いることもできる。その他の着色剤としては、液晶の電圧保持率の低下を抑制し、また、紫外線の吸収を抑制して着色スペーサーの形状や段差をコントロールしやすくするとの観点からは、有機顔料を用いることが好ましい。
なお、分散性や遮光性の点で、C.I.ピグメントバイオレット23、29が好ましく、紫外線で硬化させる場合には紫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.ピグメントバイオレット29がより好ましい。また、遮光性の観点からも、C.I.ピグメントバイオレット29が好ましい。
緑色顔料としては、C.I.ピグメントグリーン1、2、4、7、8、10、13、14、15、17、18、19、26、36、45、48、50、51、54、55を挙げることができる。この中でも、好ましくはC.I.ピグメントグリーン7、36を挙げることができる。
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。この中でも分散性、信頼性の観点から、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。
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。
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。
なお、顔料の平均粒子径は、動的光散乱(DLS)により測定された顔料粒子径から求めた値である。粒子径測定は、十分に希釈された感光性着色組成物(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。
本発明で用いる(b)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
(b1)エポキシ(メタ)アクリレート系樹脂
(b2)アクリル共重合樹脂
が優れた製版性の観点から好適に用いられる。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。
(b1)エポキシ(メタ)アクリレート系樹脂は、エポキシ化合物(エポキシ樹脂)とα,β-不飽和モノカルボン酸及び/又はエステル部分にカルボキシル基を有するα,β-不飽和モノカルボン酸エステルとの反応物の、該反応により生成した水酸基を更に多塩基酸及び/又はその無水物等の水酸基と反応し得る置換基を2個以上有する化合物とを反応させて得られる樹脂である。
また、上記、多塩基酸及び/又はその無水物を水酸基と反応させる前に、該水酸基と反応し得る置換基を2個以上有する化合物を反応させた後、多塩基酸、及び/又はその無水物を反応させて得られる樹脂も、上記(b1)エポキシ(メタ)アクリレート系樹脂に含まれる。
このように、エポキシ(メタ)アクリレート系樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「(メタ)アクリレート」に限定されるものではないが、エポキシ化合物(エポキシ樹脂)が原料であり、かつ、「(メタ)アクリレート」が代表例であるので慣用に従いこのように命名されている。
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。
<エポキシ(メタ)アクリレート系樹脂アルカリ可溶性樹脂(b1-2)>
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。
原料となるエポキシ樹脂の種類としては、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、ジシクロペンタジエンとフェノールまたはクレゾールとの重付加反応物とエピハロヒドリンとの反応生成物であるエポキシ樹脂、アダマンチル基含有エポキシ樹脂、フルオレン型エポキシ樹脂等を好適に用いることができ、このように主鎖に芳香族環を有するものを好適に用いることができる。
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。
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を前記下限値以上とすることで不飽和基の導入量の不足が抑制でき、引き続く多塩基酸及び/又はその無水物との反応も十分なものとしやすい傾向がある。一方、前記上限値以下とすることで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未反応物の残存を抑制でき、硬化特性を良好なものとしやすい傾向が認められる。
まず、前記一般式(b1-I)で表される部分構造を有するエポキシ(メタ)アクリレート系樹脂について詳述する。
前記式(b1-I)において、R12は置換基を有していてもよい2価の炭化水素基を表す。
2価の炭化水素基としては、2価の脂肪族基、2価の芳香族環基、1以上の2価の脂肪族基と1以上の2価の芳香族環基とを連結した基が挙げられる。
2価の分岐鎖状の脂肪族基としては、前述の2価の直鎖状の脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、通常1以上であり、2以上が好ましく、また、通常12以下であり、10以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環、ジシクロペンタジエン等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、ジシクロペンタジエン環、アダマンタン環から水素原子を2つ除した基が好ましい。
また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。
これらの中でもパターニング特性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、通常1以上であり、2以上が好ましく、通常10以下であり、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の芳香族環基の数は特に限定されないが、通常1以上であり、2以上が好ましく、通常10以下であり、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
これらの中でもパターニング特性の観点から、無置換であることが好ましい。
これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、ビフェニルテトラカルボン酸である。
次に、前記一般式(b1-II)で表される部分構造を有するエポキシ(メタ)アクリレート系樹脂について詳述する。
前記一般式(b1-II)において、R14は、環状炭化水素基を側鎖として有する2価の炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも感光性着色組成物の残膜率と解像性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、10以上がよりさらに好ましく、12以上が特に好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。例えば、上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、10~15が特に好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。
2価の分岐鎖状の脂肪族基としては、前述の2価の直鎖状の脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、通常1以上であり、2以上が好ましく、また、通常10以下であり、5以下が好ましく、3以下がさらに好ましい。前記下限値以上とすることで強固な膜となり、基板密着性と良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、アダマンタン環から水素原子を2つ除した基が好ましい。
また、芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの基が挙げられる。これらの中でもパターニング特性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、通常1以上であり、2以上が好ましく、通常10以下であり、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
2価の芳香族環基の数は特に限定されないが、通常1以上であり、2以上が好ましく、通常10以下であり、5以下が好ましく、3以下がより好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくく、基板への密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~10が好ましく、2~5がより好ましく、2~3がさらに好ましく挙げられる。
前記一般式(b1-II)において、R15及びR16は各々独立に、置換基を有していてもよい2価の脂肪族基を表す。
2価の分岐鎖状の脂肪族基としては、前述の2価の直鎖状の脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、tert-ブチル基等を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、通常1以上であり、2以上が好ましく、また、通常12以下であり、10以下が好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、1~12が好ましく、2~10がより好ましく挙げられる。
2価の環状の脂肪族基の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環、ジシクロペンタジエン等の環から水素原子を2つ除した基が挙げられる。これらの中でも骨格の剛直性の観点から、ジシクロペンタジエン環、アダマンタン環から水素原子を2つ除した基が好ましい。
前記一般式(b1-II)において、m及びnは各々独立に0~2の整数を表す。前記下限値以上とすることでパターニング適正が良好となり、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。現像性の観点からm及びnが0であることが好ましい。一方で、パターニング適正、表面荒れの観点からm及びnが1以上であることが好ましい。
前記一般式(b1-II-1)において、Rαは、置換基を有していてもよい1価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。例えば、上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、8~15が特に好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としてはシクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも強固な膜特性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常4以上であり、5以上が好ましく、6以上がより好ましく、また、30以下が好ましく、20以下がより好ましく、15以下がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることでパターニング特性が良好となる傾向がある。例えば、上限と下限の組み合わせとしては、4~30が好ましく、5~20がより好ましく、6~15がさらに好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像溶解性の観点から、フルオレン環が好ましい。
これらの中でもパターニング特性の観点から、無置換であることが好ましい。
前記式(b1-II-2)において、Rβは、置換基を有していてもよい2価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
また、脂肪族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、また、40以下が好ましく、35以下がより好ましく、30以下がさらに好ましい。前記下限値以上とすることで現像時の膜あれを抑制する傾向があり、また、前記上限値以下とすることで感度の悪化や現像時の膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、4~40が好ましく、6~35がより好ましく、8~30がさらに好ましく挙げられる。
脂肪族環基における脂肪族環の具体例としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等が挙げられる。これらの中でも現像時の膜減り、解像性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常4以上であり、6以上が好ましく、8以上がより好ましく、10以上がさらに好ましく、また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで感度の悪化や膜減りを抑制しやすく、解像性が向上する傾向がある。例えば、上限と下限の組み合わせとしては、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、10~15が特に好ましく挙げられる。
芳香族環基における芳香族環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環等が挙げられる。これらの中でも現像性の観点から、フルオレン環が好ましい。
一方で、パターニング特性の観点から、Rβが2価の芳香族環基であることが好ましく、2価のフルオレン環基であることがより好ましい。
また、置換基を介して2つのベンゼン環が連結していてもよい。この場合の置換基としては、-O-、-S-、-NH-、-CH2-等の2価の基が挙げられる。
これらの中でもパターニング特性の観点から、無置換であることが好ましい。また、膜減り等を生じにくくする観点から、メチル基置換であることが好ましい。
多塩基酸としては、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた1種又は2種以上が挙げられる。
これらの中でもパターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、ビフェニルテトラカルボン酸である。
また、前述のエポキシ(メタ)アクリレート系樹脂の一部を、他のバインダー樹脂に置き換えて用いてもよい。即ち、エポキシ(メタ)アクリレート系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、(b)アルカリ可溶性樹脂におけるエポキシ(メタ)アクリレート系樹脂の割合を、50質量%以上とすることが好ましく、60質量%以上とすることがより好ましく、70質量%以上とすることがさらに好ましく、80質量%以上とすることが特に好ましく、通常100質量%以下である。
例えば、上限と下限の組み合わせとしては、50~100質量%が好ましく、60~100質量%がより好ましく、70~100質量%がさらに好ましく、80~100質量%が特に好ましく挙げられる。
不飽和単量体(b2-1)としては、例えば、(メタ)アクリル酸、クロトン酸、α-クロルアクリル酸、けい皮酸等の不飽和モノカルボン酸;マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸又はその無水物;こはく酸モノ〔2-(メタ)アクリロイロキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイロキシエチル〕等の2価以上の多価カルボン酸のモノ〔(メタ)アクリロイロキシアルキル〕エステル;ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート;p-ビニル安息香酸等を挙げることができる。
これらの不飽和単量体(b2-1)は、単独で又は2種以上を混合して使用することができる。
スチレン、α-メチルスチレン、p-ヒドロキシスチレン、p-ヒドロキシ-α-メチルスチレン、p-ビニルベンジルグリシジルエーテル、アセナフチレン等の芳香族ビニル化合物;
ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー等を挙げることができる。
これらの不飽和単量体(b2-2)は、単独で又は2種以上を混合して使用することができる。
不飽和単量体(b2-1)と不飽和単量体(b2-2)の共重合体は、公知の方法により製造することができるが、例えば、日本国特開2003-222717号公報、日本国特開2006-259680号公報、国際公開第2007/029871号等に開示されている方法により、その構造やMw、Mw/Mnを制御することもできる。
(c)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;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系化合物等が挙げられる。
アルキル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基、4-(2-メトキシ-1-メチル)エトキシ-2-メチルフェニル基又はN-アセチル-N-アセトキシアミノ基などが挙げられ、合成容易性の観点からは、無置換であることが好ましい。
芳香族環基が有していてもよい置換基としては、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基、アルキル基、アルコキシ基、これらの置換基が連結した基などが挙げられ、現像性の観点からアルキル基、アルコキシ基、これらを連結した基が好ましく、連結したアルコキシ基がより好ましい。
これらの中でも、現像性の観点から、R21aが置換基を有していてもよい芳香族環基であることが好ましく、連結したアルコキシ基を置換基に有する芳香族環基であることがさらに好ましい。
アルカノイル基の具体例としては、アセチル基、プロパノイル基、ブタノイル基等が挙げられる。
アルカノイル基が有していてもよい置換基としては、芳香族環基、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基などが挙げられ、合成容易性の観点からは、無置換であることが好ましい。
アリーロイル基が有していてもよい置換基としては、水酸基、カルボキシル基、ハロゲン原子、アミノ基、アミド基、アルキル基などが挙げられ、合成容易性の観点からは、無置換であることが好ましい。
これらの中でも、感度の観点から、R22aが置換基を有していてもよいアルカノイル基であることが好ましく、無置換のアルカノイル基であることがより好ましく、アセチル基であることがさらに好ましい。
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号公報、日本国特開平4-219756号公報に記載のキサンテン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の複素環を有するクマリン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の3-ケトクマリン化合物、日本国特開平6-19240号公報に記載のピロメテン色素、その他、日本国特開昭47-2528号公報、日本国特開昭54-155292号公報、日本国特公昭45-37377号公報、日本国特開昭48-84183号公報、日本国特開昭52-112681号公報、日本国特開昭58-15503号公報、日本国特開昭60-88005号公報、日本国特開昭59-56403号公報、日本国特開平2-69号公報、日本国特開昭57-168088号公報、日本国特開平5-107761号公報、日本国特開平5-210240号公報、日本国特開平4-288818号公報に記載のジアルキルアミノベンゼン骨格を有する色素等を挙げることができる。
増感色素は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の感光性着色組成物は、(d)エチレン性不飽和化合物を含む。(d)エチレン性不飽和化合物を含むことで、感度が向上する。
本発明に用いられるエチレン性不飽和化合物は、分子内にエチレン性不飽和基を少なくとも1個有する化合物である。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。
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。
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。
本発明の感光性着色組成物は、(e)溶剤を含む。(e)溶剤を含むことで、(a)着色剤を溶剤中に溶解又は分散でき、また、塗布が容易となる。
本発明の感光性着色組成物は、通常、(a)着色剤、(b)アルカリ可溶性樹脂、(c)光重合開始剤、(d)エチレン性不飽和化合物、(f)分散剤、及び必要に応じて使用されるその他の各種材料が、溶剤に溶解又は分散した状態で使用される。溶剤の中でも、分散性や塗布性の観点から有機溶剤が好ましい。
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-メトキシブタノール、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;
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;
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;
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。
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。
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、後に得られる感光性着色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。
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。
本発明の感光性着色組成物においては、(a)着色剤を微細に分散させ、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、(f)分散剤を含む。
(f)分散剤としては、官能基を有する高分子分散剤が好ましく、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;四級アンモニウム塩基;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、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基;四級アンモニウム塩基;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特に好ましい。
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。
これらの内、顔料の分散性の観点から、(f)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。
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300~10000の化合物と、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1000~200000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。
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。
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。
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。
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。
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。
ウレタン系高分子分散剤の重量平均分子量(Mw)は通常1000~200000、好ましくは2000~100000、より好ましくは3000~50000の範囲である。前記下限値以上とすることで分散性及び分散安定性が良好となる傾向があり、前記上限値以下とすることで溶解性や分散性の低下を抑制しやすい傾向がある。
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。
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、この範囲内にすることで良好な分散性を確保できる傾向がある。
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。上限と下限の組み合わせとしては、10~90mgKOH/gが好ましく、30~80mgKOH/gがより好ましく、50~75mgKOH/gがさらに好ましく挙げられる。
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。
〔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アミン価は、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、1000~100000の範囲が好ましい。前記範囲内とすることで良好な分散性を確保できる傾向がある。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。
アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。
アラルキル基の具体例としては、フェニルメチル基(ベンジル基)、フェニルエチル基(フェネチル基)、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。
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。
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。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。
アルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基などが挙げられ、これらの中でも、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、又はヘキシル基であることが好ましく、メチル基、エチル基、プロピル基、又はブチル基であることがより好ましい。また、直鎖状、分岐鎖状のいずれであってもよい。また、シクロヘキシル基、シクロヘキシルメチル基などの環状構造を含んでもよい。
アリール基の具体例としては、フェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ナフチル基、アントラセニル基などが挙げられ、これらの中でもフェニル基、メチルフェニル基、エチルフェニル基、ジメチルフェニル基、又はジエチルフェニル基であることが好ましく、フェニル基、メチルフェニル基、又はエチルフェニル基であることがより好ましい。
アラルキル基の具体例としては、フェニルメチル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルイソプロピル基などが挙げられ、これらの中でも、フェニルメチル基、フェニルエチル基、フェニルプロピル基、又はフェニルブチル基であることが好ましく、フェニルメチル基、又はフェニルエチル基であることがより好ましい。
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。
本発明の感光性着色組成物には、上述の成分の他、シランカップリング剤等の密着向上剤、界面活性剤(塗布性向上剤)、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、重合禁止剤、現像改良剤、紫外線吸収剤、酸化防止剤等の添加剤を適宜配合することができる。
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種単独で、或いは2種以上を混合して使用できる。
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。
これらの燐酸基含有化合物は、1種単独で用いても、2種以上を併用してもよい。
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。
このような界面活性剤としては、例えば、TSF4460(モメンティブ・パフォーマンス・マテリアルズ社製)、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(東レ・ダウコーニング社製)、DS-401(ダイキン社製)、L-77(日本ユニカー社製)、FC4430(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。
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。
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。
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。
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。
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。
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。
本発明の感光性着色組成物には、形状制御の観点から、重合禁止剤を含有させてもよい。重合禁止剤を含有することでそれが塗布膜下層のラジカル重合を阻害することから、テーパー角(硬化物断面に於ける支持体と硬化物のなす角度)を制御できると考えられる。
重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルヒドロキノン、メトキシフェノール、2,6-ジ-tert-ブチル-4-クレゾール(BHT)などが挙げられる。これらの中でも形状制御の観点から、2,6-ジ-tert-ブチル-4-クレゾールが好ましい。また人体への安全性の観点から、ハイドロキノンモノメチルエーテル、メチルヒドロキノンが好ましい。
重合禁止剤は、1種又は2種以上を含有することが好ましい。(b)アルカリ可溶性樹脂を製造する際に、当該樹脂中に重合禁止剤が含まれることがあり、それを本発明の重合禁止剤として用いてもよいし、樹脂中に重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性着色組成物製造時に添加してもよい。
本発明の感光性着色組成物において、(a)着色剤の含有割合は特に限定されないが、感光性着色組成物中の全固形分中に通常10質量%以上であり、20質量%以上であることがより好ましく、25質量%以上であることがさらに好ましく、30質量%以上であることがよりさらに好ましく、32質量%以上であることが特に好ましく、35質量%以上であることが最も好ましく、また、60質量%以下であることが好ましく、50質量%以下であることがより好ましく、45質量%以下であることがさらに好ましく、40質量%以下であることがよりさらに好ましく、38質量%以下であることが特に好ましく、35質量%以下であることが最も好ましい。(a)着色剤の含有割合を前記下限値以上とすることで、十分な遮光性が得られる傾向があり、また、前記上限値以下とすることで十分な製版特性が得られやすく、また電気信頼性が優れる傾向がある。例えば、上限と下限の組み合わせとしては、10~60質量%が好ましく、20~50質量%がより好ましく、25~45質量%が次に好ましく、30~40質量%がさらに好ましく、32~38質量%がよりさらに好ましく、35~38質量%が特に好ましく挙げられる。
(a3)カーボンブラック100質量部に対する(a1)有機黒色顔料の含有割合は通常150質量部以上であり、180質量部以上であることが好ましく、200質量部以上であることがより好ましく、210質量部以上であることが次に好ましく、220質量部以上であることがさらに好ましく、250質量部以上であることがよりさらに好ましく、300質量部以上であることが殊更に好ましく、350質量部以上であることがより殊更に好ましく、400質量部以上であることがさらに殊更に好ましく、450質量部以上が特に好ましく、480質量部以上が最も好ましい。また、1000質量部以下であることが好ましく、800質量部以下であることがより好ましく、600質量部以下であることがさらに好ましく、500質量部以下であることが特に好ましい。前記下限値以上とすることで近赤外領域での透過率が高くなる傾向があり、前記上限値以下とすることで電気信頼性が高くなる傾向がある。例えば、上限と下限の組み合わせとしては、150~1000質量部が好ましく、180~800質量部がより好ましく、200~800質量部が次に好ましく、210~600質量部がさらに好ましく、220~600質量部がよりさらに好ましく、250~600質量部が殊更に好ましく、300~600質量部がより殊更に好ましく、350~600質量部がさらに殊更に好ましく、400~600質量部が次に殊更に好ましく、450~500質量部が特に好ましく、480~500質量部が最も好ましく挙げられる。
(a3)カーボンブラック100質量部に対する全有機顔料の含有割合は、通常300質量部以上、400質量部以上が好ましく、500質量部以上がより好ましく、550質量部以上がさらに好ましく、600質量部以上がよりさらに好ましく、620質量部以上が特に好ましく、650質量部以上が最も好ましく、また、900質量部以下が好ましく、800質量部以下がより好ましい。前記下限値以上とすることで波長900nm付近の透過率が高くなる傾向があり、また、前記上限値以下とすることで十分な遮光性が得られ、また、波長700nm付近の光漏れを抑制できる傾向がある。例えば、上限と下限の組み合わせとしては、300~900質量部が好ましく、400~900質量部がより好ましく、500~900質量部が次に好ましく、550~800質量部がさらに好ましく、600~800質量部がよりさらに好ましく、620~800質量部が特に好ましく、650~800質量部が最も好ましく挙げられる。
(a3)カーボンブラック100質量部に対する(a2)C.I.ピグメントブルー60の含有割合は、50質量部以上が好ましく、100質量部以上がより好ましく、150質量部以上がさらに好ましく、180質量部以上がよりさらに好ましく、200質量部以上が殊更に好ましく、210質量部以上がより殊更に好ましく、220質量部以上が特に好ましく、240質量部以上が最も好ましく、また、400質量部以下が好ましく、300質量部以下がより好ましい。前記下限値以上とすることで波長700nm付近の光漏れを抑制できる傾向があり、また、前記上限値以下とすることで波長900nm付近の透過率が高くなる傾向がある。例えば、上限と下限の組み合わせとしては、50~400質量部が好ましく、100~400質量部がより好ましく、150~400質量部がさらに好ましく、200~300質量部がよりさらに好ましく、220~300質量部が特に好ましく、240~300質量部が最も好ましく挙げられる。
(a1)有機黒色顔料100質量部に対する紫色顔料の含有割合は、10質量部以上が好ましく、20質量部以上がより好ましく、40質量部以上がさらに好ましく、55質量部以上がよりさらに好ましく、60質量部以上が殊更に好ましく、65質量部以上が特に好ましく、70質量部以上が最も好ましく、また、100質量部以下が好ましく、90質量部以下がより好ましく、80質量部以下がさらに好ましく、70質量部以下がよりさらに好ましく、65質量部以下が特に好ましい。前記下限値以上とすることで十分な遮光性を確保でき、また、信頼性が向上する傾向があり、また、前記上限値以下とすることで波長700nm付近の光漏れを抑制できる傾向がある。例えば、上限と下限の組み合わせとしては、10~100質量部が好ましく、20~100質量部がより好ましく、40~100質量部が次に好ましく、55~100質量部がさらに好ましく、60~100質量部がよりさらに好ましく、65~90質量部が特に好ましく、70~90質量部が最も好ましく挙げられる。
また、(c)光重合開始剤と共に増感色素を用いる場合、その含有割合は特に限定されないが、感度の観点から感光性着色組成物中の全固形分中に通常20質量%以下、好ましくは15質量%以下、より好ましくは10質量%以下である。
本発明の感光性着色組成物は、着色スペーサー形成用に好適に使用することができ、着色スペーサーとして用いるとの観点からは黒色を呈していることが好ましい。また、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く、1.2以上であることがより好ましく、1.3以上であることがさらに好ましく、1.4以上であることがよりさらに好ましく、1.5以上であることが特に好ましく、1.8以上であることが最も好ましく、通常4.0以下であり、3.0以下であることが好ましく、2.5以下であることがより好ましい。例えば、上限と下限の組み合わせとしては、1.0~4.0が好ましく、1.2~3.0がより好ましく、1.3~3.0がさらに好ましく、1.4~3.0がよりさらに好ましく、1.5~3.0が特に好ましく、1.8~2.5が最も好ましく挙げられる。
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)着色剤は、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)着色剤が微粒子化されるため、レジストの塗布特性が向上する。
このように、レジストを製造する工程において、(a)着色剤、(e)溶剤、及び(f)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)着色剤、(e)有機溶剤、及び(f)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。また、顔料分散液における(a)着色剤の各着色剤の含有割合としても、感光性着色組成物における含有割合として記載したものを好ましく採用することができる。
サンドグラインダーで(a)着色剤を分散させる場合には、0.1~8mm程度の粒子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。
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あるため、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。
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、着色スペーサーとして好適に用いることができる。
次に、本発明の感光性着色組成物を用いた着色スペーサーについて、その製造方法に従って説明する。
着色スペーサー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。主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。
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。
本発明の感光性着色組成物は、公知のカラーフィルター用感光性着色組成物と同様の用途に使用されるが、以下、着色スペーサー(ブラックフォトスペーサー)として使用される場合について、本発明の感光性着色組成物を用いたブラックフォトスペーサーの形成方法の具体例に従って説明する。
[1]基板への供給方法
本発明の感光性着色組成物は、通常、溶剤に溶解或いは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法などによって行うことができる。また、インクジェット法や印刷法などにより、パターン状に供給されてもよい。中でも、ダイコート法によれば、塗布液の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くない、異物発生が抑制されるなど、総合的な観点から好ましい。
基板上に感光性着色組成物溶液を供給した後の乾燥は、ホットプレート、IRオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。また、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。
露光は、感光性着色組成物の塗布膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを感光性着色組成物の塗布膜に近接させる方法や、露光マスクを感光性着色組成物の塗布膜から離れた位置に配置し、該露光マスクを介した露光光を投影する方法によってもよい。また、マスクパターンを用いないレーザー光による走査露光方式によってもよい。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ったりしてもよい。
中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作成する方法等が知られている。また吸収体として、クロム系、モリブデン系、タングステン系、シリコン系などの材料の膜によって、光透過率を制御し作成する方法等が知られている。
また、近接露光方式の場合には、露光対象とマスクパターンとの距離としては、通常10μm以上、好ましくは50μm以上、より好ましくは75μm以上であり、通常500μm以下、好ましくは400μm以下、より好ましくは300μm以下である。
上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。この水溶液には、さらに界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。
現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行ってもよく、また熱硬化処理を行ってもよい。この際の熱硬化処理条件は、温度は100℃~280℃の範囲、好ましくは150℃~250℃の範囲で選ばれ、時間は5分間~60分間の範囲で選ばれる。
また、本発明の着色スペーサーの1μm当たりの光学濃度(OD)は、遮光性の観点から、1.2以上が好ましく、1.5以上がより好ましく、1.8以上がさらに好ましく、通常4.0以下であり、3.0以下であることが好ましい。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。例えば、上限と下限の組み合わせとしては、1.2~4.0が好ましく、1.5~3.0がより好ましく、1.8~3.0がさらに好ましく挙げられる。
カラーフィルターは、液晶駆動基板(アレイ基板)上に、赤色、緑色、青色の画素着色層を形成することができる。あるいは透明基板としてのガラス基板上に、画素着色層を形成してもよい。
本発明の画像表示装置は、上述のような本発明の着色スペーサーを備えるものである。
例えば、本発明の着色スペーサーを有する液晶駆動基板(アレイ基板)上に配向膜を形成し、対極基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入することで、本発明の着色スペーサーを備えた、液晶表示装置等の画像表示装置を製造することができる。
一方で、本発明の着色スペーサーを対極基板側に設置し、液晶駆動基板(アレイ基板)と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入することでも、本発明の着色スペーサーを備えた、液晶表示装置等の画像表示装置を製造することができる。
また例えば、特開2014-215614号公報に記載されているように、特定の配向物質を用い、液晶セルに液晶を注入した後に紫外線を照射することで、液晶配向性を向上させることができる。
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。
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メタクリレート(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。
日本化薬社製「ZCR-1664H」(Mw=6500、酸価=60mgKOH、/g)
BASF社製、「Irgaphor(登録商標) Black S 0100 CF」(下記式(I-1)で表される化学構造を有する)。これは着色剤(a1)に該当する。
C.I.ピグメントブルー60。これは着色剤(a2)に該当する。
カーボンブラック。ビルラー社製「RAVEN1060U」(旧コロンビア社製「R1060」)。これは着色剤(a3)に該当する。
C.I.ピグメントブルー15:6。
<顔料-V>
C.I.ピグメントバイオレット29。
<顔料-VI>
BASF社製、「Paliogen(登録商標) Black L0086」。ペリレンブラック。着色剤(a1)以外の有機黒色顔料。
ビックケミー社製「BYK-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3級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Aブロック中には、下記式(1a)及び(2a)の繰り返し単位が含まれ、Bブロック中には下記式(3a)の繰り返し単位が含まれる。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。
ビックケミー社製「DISPERBYK-167」(ウレタン系高分子分散剤)
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-1-ブタノール
以下に記載の化学構造を有するオキシムエステル開始剤。
DPHA:日本化薬社製 ジペンタエリスリトールヘキサアクリレート
<添加剤>
日本化薬社製、「KAYAMER PM-21」(メタクリロイル基含有ホスフェート)
<界面活性剤>
DIC社製 「メガファック 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。この混合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、2、4、5及び6を調製した。なお、顔料-VIを顔料分散液2と同じ条件で分散したところ粘度が大きく増加したため、顔料分散液6では顔料に対する分散剤の含有割合を高く設定する必要があった。
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、分散処理時間を6時間に変更した以外は、顔料分散液1、2、4、5及び6と同様の方法で分散を行い、顔料分散液3を調製した。
上記調製した顔料分散液1~6を用いて、固形分中の比率が表2~5の配合割合となるように他の各成分を加え、さらに全固形分の含有割合が19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、以下の方法にて評価を行った。
単位膜厚当たりの光学濃度は以下の手順にて測定した。
まず、調製した各感光性着色組成物をポストベーク後の膜厚が2.5μm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90℃にて90秒間乾燥した。その後、高圧水銀灯を用い400mJ/cm2、照度45mW/cm2の露光条件にて全面露光を行い、230℃で20分間加熱(ポストベーク)する事で、レジスト塗工基板を得た。得られた基板の光学濃度(OD値)を透過濃度計グレタグマクベスD200-IIによって測定し、膜厚を菱化システム社製非接触表面・層断面形状計測システム VertScan(R)2.0により測定し、光学濃度(OD値)及び膜厚から、単位膜厚(1μm)当たりの光学濃度(単位OD値)を算出した。なお、OD値は遮光能力を示す数値であり、数値が大きいほど高遮光性であることを示す。
波長700nmの透過率は光漏れの指標となり、数値が小さい程好ましい。2.5%以下であれば好ましい傾向がある。
また波長900nmの透過率はマスク位置合わせのためのマークの読み取り適性の指標となり、数値が大きい程好ましい。10%以上であれば好ましい傾向がある。
単位OD値及び透過率の測定結果を表2~5に示す。
以下に記載した方法により、電圧保持率(VHR)、イオン密度の評価を行った。
片全面にITO膜を形成した電極基板A(EHC社製、評価用ガラスITO片全面被覆)と、ガラス基板の片面中央部に2mm幅の取り出し電極がつながった1cm角のITO膜(2)を形成した電極基板B(20)(EHC社製、評価用ガラスSZ-B111MIN(B))を用意した。図1に電極基板B(20)の上面の模式図を示す。
その後、評価用電極基板B(9)の外周上に、ディスペンサーを用いて、直径5μmのシリカビーズを含有するエポキシ樹脂系シール剤(5)を塗布した後、評価用電極基板B(9)の表側(シール剤側)に評価用電極基板A(8)の塗布面を圧着したまま貼り付けて、空セルを作成した。作成した空セルを熱風循環炉内で180℃、2時間加熱した。
作成した測定用液晶セルに電圧5Vで、2.0Hz、フレーム時間1667msecの条件で電圧印加し、東陽テクニカ社製「液晶物性評価装置-6254型」にて電圧保持率を測定し、電気信頼性の指標として評価した。なお電圧保持率は高いほど好ましい。結果を表2~5に示した。
また、周波数を0.6Hzに変更した以外は同条件にて電圧保持率を測定した。結果を表2、4及び5に示した。
イオン密度は、例えばInternational Display Workshop(IDW)‘06予稿集LCT7-1にも記載されている方法で測定することができる。イオン密度測定は徐々に電圧を印加するため、イオンピークと液晶配向ピークを区別して測定でき、電圧保持率では差が出にくい信頼性の差を測定できる場合がある。不純物イオンは、液晶表示装置においては残像、フリッカー(ちらつき)等表示不良の原因となる場合があり、イオン密度測定はその評価に有効である。
また比較例2、3の感光性着色組成物を用いた塗布基板は波長700nmの透過率が高く、長波長領域の可視光の遮光性が不十分であり、光漏れが生じていることが確認された。また比較例2の感光性着色組成物を用いた塗布基板は紫外線照射後の2.0Hzにおける電圧保持率が低いことから、液晶駆動を阻害するものであることが確認された。
一方で比較例4の感光性着色組成物を用いた塗布基板は、波長900nmの透過率及び波長700nmの透過率に問題はなかったが、紫外線照射後の2.0Hzにおける電圧保持率が低いことから、液晶駆動を阻害するものであることが確認された。
2 ITO膜
3 着色硬化膜
4 ポリイミド膜
5 エポキシ樹脂系シール剤
6 UV硬化型シール剤
7 液晶
8 評価用電極基板A
9 評価用電極基板B
11 印加電圧値
12 測定電流値
13 不純物イオンピーク部
20 電極基板B
30 測定用液晶セル
Claims (12)
- (a)着色剤、(b)アルカリ可溶性樹脂、(c)光重合開始剤、(d)エチレン性不飽和化合物、(e)溶剤、及び(f)分散剤を含有する感光性着色組成物であって、
前記(a)着色剤が、(a1)下記一般式(I)で表される化合物、前記化合物の幾何異性体、前記化合物の塩、及び前記化合物の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料、(a2)C.I.ピグメントブルー60、並びに(a3)カーボンブラックを含み、
前記(a3)カーボンブラック100質量部に対する前記(a1)有機黒色顔料の含有割合が150質量部以上であることを特徴とする感光性着色組成物。
(式(I)中、R1及びR6は各々独立に水素原子、CH3、CF3、フッ素原子又は塩素原子であり;
R2、R3、R4、R5、R7、R8、R9及びR10は各々独立に水素原子、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又はSO2NR11R12であり;
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、互いに直接結合することもでき、又は酸素原子、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;
R11及びR12は各々独立に、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又は炭素数2~12のアルキニル基である。) - 前記(a3)カーボンブラック100質量部に対する前記(a1)有機黒色顔料の含有割合が200質量部以上である、請求項1に記載の感光性着色組成物。
- 前記(a3)カーボンブラック100質量部に対する前記(a1)有機黒色顔料の含有割合が210質量部以上である、請求項1又は2に記載の感光性着色組成物。
- 前記(a3)カーボンブラック100質量部に対する前記(a2)C.I.ピグメントブルー60の含有割合が200質量部以上である、請求項1~3のいずれか1項に記載の感光性着色組成物。
- 前記(a3)カーボンブラック100質量部に対する全有機顔料の含有割合の合計が550質量部以上である、請求項1~4のいずれか1項に記載の感光性着色組成物。
- 前記(a)着色剤の含有割合が全固形分中10質量%以上である、請求項1~5のいずれか1項に記載の感光性着色組成物。
- 前記(a)着色剤の含有割合が全固形分中45質量%以下である、請求項1~6のいずれか1項に記載の感光性着色組成物。
- 前記(b)アルカリ可溶性樹脂が、(b1)エポキシ(メタ)アクリレート系樹脂を含有する、請求項1~7のいずれか1項に記載の感光性着色組成物。
- 硬化した塗膜の膜厚1μm当たりの光学濃度が1.0以上である、請求項1~8のいずれか1項に記載の感光性着色組成物。
- 請求項1~9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。
- 請求項10に記載の硬化物から形成される着色スペーサー。
- 請求項11に記載の着色スペーサーを備える画像表示装置。
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TW201835682A (zh) | 2018-10-01 |
KR20180113222A (ko) | 2018-10-15 |
CN110178083A (zh) | 2019-08-27 |
KR101980062B1 (ko) | 2019-05-17 |
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