CN110178083B - Photosensitive coloring composition, cured product, coloring spacer and image display device - Google Patents

Photosensitive coloring composition, cured product, coloring spacer and image display device Download PDF

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CN110178083B
CN110178083B CN201880006278.6A CN201880006278A CN110178083B CN 110178083 B CN110178083 B CN 110178083B CN 201880006278 A CN201880006278 A CN 201880006278A CN 110178083 B CN110178083 B CN 110178083B
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CN110178083A (en
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泽井良尚
裴丽华
伊藤敦哉
土谷达格
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Mitsubishi Chemical Corp
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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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • 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)
    • 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

Abstract

The invention provides a photosensitive coloring composition which has little light leakage near the wavelength of 700nm, excellent transmissivity near the wavelength of 900nm and excellent electrical reliability after ultraviolet irradiation. The photosensitive coloring composition of the invention comprises: a colorant (a), an alkali-soluble resin (b), a photopolymerization initiator (c), an ethylenically unsaturated compound (d), a solvent (e), and a dispersant (f), wherein the colorant (a) comprises: (a1) An organic black pigment comprising at least one member 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, (a 2) C.I. pigment blue 60, and (a 3) carbon black, wherein the content of the organic black pigment (a 1) is 150 parts by mass or more per 100 parts by mass of the carbon black (a 3).
Figure DDA0002123220610000011

Description

Photosensitive coloring composition, cured product, coloring spacer and image display device
Technical Field
The present invention relates to a photosensitive coloring composition and the like. More specifically, the present invention relates to a photosensitive coloring composition preferably used for forming a color 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, a color spacer formed from the cured product, and an image display device provided with the color spacer.
The entire contents of the specification, claims, drawings, and abstract of japanese patent application 2017-026369 filed on the sun in 2017, 2 and 15, and japanese patent application 2017-166318 filed on the sun in 2017, 8 and 31, and part or all of the contents disclosed in documents and the like cited in the specification are incorporated herein as the disclosure of the specification.
Background
A Liquid Crystal Display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by on/off of a voltage applied to the liquid crystal. On the other hand, many of the members constituting the unit of the LCD are formed by a method using a photosensitive composition typified by photolithography. The photosensitive composition tends to be more widely applicable in the future because of its ease of forming a fine structure and its ease of processing a substrate for a large screen.
However, in the LCD manufactured using the photosensitive composition, the voltage applied to the liquid crystal cannot be maintained due to the influence of the electrical characteristics of the photosensitive composition itself and impurities contained in the photosensitive composition, and thus, there is a problem that display unevenness of the display or the like occurs. In particular, the influence of a member close to the liquid crystal layer in a color liquid crystal display, for example, a member used for keeping the interval between 2 substrates constant in a liquid crystal panel, that is, a so-called column spacer, a photo spacer, or the like, is significant.
Conventionally, when a spacer having no light-shielding property is used in a TFT-type LCD, a TFT as a switching element may malfunction due to light transmitted through the spacer. In order to prevent this, a method using a spacer having a light-shielding property (colored spacer) has been studied.
On the other hand, in recent years, along with the change in panel structure, a method of forming colored spacers having different heights at a time by photolithography has been proposed. For example, patent document 1 discloses that a specific black pigment species is used, thereby achieving excellent light-shielding properties, dispersibility, and platemaking properties and achieving sufficiently low conductivity.
In addition, patent document 2 discloses a colored photosensitive resin composition which has excellent elastic recovery, resolution, and chemical resistance and also satisfies the characteristics of a black matrix by using a plurality of organic colored pigments as pigments.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/046178
Patent document 2: korean laid-open patent No. 10-2014-0096423
Disclosure of Invention
Problems to be solved by the invention
With the change of the panel structure in recent years, it is sometimes necessary for the colored spacer not to generate light leakage at a wavelength around 700nm and to secure transmittance at a wavelength around 900nm so that a mark for determining the mask position can be recognized at the time of exposure.
On the other hand, a method of irradiating ultraviolet rays after fabricating a liquid crystal cell in order to improve liquid crystal alignment properties has been widely used. When ultraviolet irradiation is performed, a part of the pigment or its treatment agent tends to be decomposed to generate impurities, and in this case, it is required to maintain sufficient electrical reliability.
The inventors of the present invention have studied the photosensitive coloring composition described in patent document 1 and found that it is difficult to suppress light leakage at a wavelength of about 700nm and to ensure transmittance of light at a wavelength of about 900 nm.
In addition, when the photosensitive coloring composition described in patent document 2 is studied, it has been found that it is difficult to ensure electrical reliability particularly after ultraviolet irradiation.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive coloring composition which has less light leakage at a wavelength of around 700nm, has excellent transmittance of light at a wavelength of around 900m, and has excellent poor electrical reliability after ultraviolet irradiation.
Means for solving the problems
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific organic black pigment, c.i. pigment blue 60 and carbon black in a photosensitive coloring composition and setting the content ratio of the specific organic black pigment to the carbon black within a specific range, and have completed the present invention.
That is, the present invention has the following configurations [1] to [12 ].
[1] A photosensitive coloring composition, comprising: a colorant (a), an alkali-soluble resin (b), a photopolymerization initiator (c), an ethylenically unsaturated compound (d), a solvent (e), and a dispersant (f), wherein,
the (a) colorant comprises: (a1) An organic black pigment comprising at least one member 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, (a 2) C.I. pigment blue 60, and (a 3) carbon black,
the content of the organic black pigment (a 1) is 150 parts by mass or more per 100 parts by mass of the carbon black (a 3).
[ chemical formula 1]
Figure BDA0002123220590000031
(in the formula (I), R 1 And R 6 Each independently is a hydrogen atom, CH 3 、CF 3 Fluorine atom or chlorine atom;
R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R 10 Each independently is a hydrogen atom, a halogen atom, R 11 、COOH、COOR 11 、COO - 、CONH 2 、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH 2 、OOCNHR 11 、OOCNR 11 R 12 、NO 2 、NH 2 、NHR 11 、NR 11 R 12 、NHCOR 12 、NR 11 COR 12 、N＝CH 2 、N＝CHR 11 、N＝CR 11 R 12 、SH、SR 11 、SOR 11 、SO 2 R 11 、SO 3 R 11 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 11 Or SO 2 NR 11 R 12 ；
And is selected from R 2 And R 3 、R 3 And R 4 、R 4 And R 5 、R 7 And R 8 、R 8 And R 9 And R 9 And R 10 Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR 21 Bridging to bond each other;
R 11 and R 12 Each independently is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms. )
[2] The photosensitive coloring composition according to [1], wherein the content of the organic black pigment (a 1) is 200 parts by mass or more per 100 parts by mass of the carbon black (a 3).
[3] The photosensitive coloring composition according to [1] or [2], wherein the content of the organic black pigment (a 1) is 210 parts by mass or more per 100 parts by mass of the carbon black (a 3).
[4] The photosensitive coloring composition according to any one of the above [1] to [3], wherein the content of the (a 2) C.I. pigment blue 60 is 200 parts by mass or more per 100 parts by mass of the (a 3) carbon black.
[5] The photosensitive coloring composition according to any one of the above [1] to [4], wherein the total content of all organic pigments is 550 parts by mass or more per 100 parts by mass of the carbon black (a 3).
[6] The photosensitive coloring composition according to any one of the above [1] to [5], wherein the content of the colorant (a) is 10% by mass or more of the total solid content.
[7] The photosensitive coloring composition according to any one of the above [1] to [6], wherein a content ratio of the colorant (a) is 45% by mass or less in the entire solid content.
[8] The photosensitive coloring composition according to any one of the above [1] to [7], wherein the alkali-soluble resin (b) contains an epoxy (meth) acrylate resin (b 1).
[9] The photosensitive coloring composition according to any one of the above [1] to [8], wherein an average optical density per 1 μm film thickness of a coating film after curing is 1.0 or more.
[10] A cured product obtained by curing the photosensitive coloring composition according to any one of the above [1] to [9 ].
[11] A colored spacer formed from the cured product of [10 ].
[12] An image display device comprising the colored spacer of [11 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a photosensitive colored composition, a cured product, and a colored spacer, which are less in light leakage at a wavelength of around 700nm, excellent in transmittance of light at a wavelength of around 900nm, and excellent in electrical reliability after ultraviolet irradiation, and can also provide an image display device provided with such a colored spacer.
Drawings
Fig. 1 is a schematic view of the upper surface of an electrode substrate B used in the examples.
FIG. 2 is a schematic side view of a liquid crystal cell for measurement used in the examples.
Fig. 3 is a schematic diagram of a waveform of an applied voltage of 1 cycle in ion density measurement and a schematic diagram of a waveform of a measurement current.
Description of the symbols
1. Glass
2 ITO film
3. Colored cured film
4. Polyimide film
5. Epoxy resin sealing agent
6 UV-curable sealant
7. Liquid crystal display device
8. Electrode substrate for evaluation A
9. Electrode substrate B for evaluation
11. Value of applied voltage
12. Measuring the current value
13. Impurity ion peak
20. Electrode substrate B
30. Liquid crystal cell for measurement
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth) acryl" means "acryl and/or methacryl", "(meth) acrylate" and "(meth) acryl" are also the same.
The meaning of the "(co) polymer" includes both homopolymer (homopolymer) and copolymer (copolymer), and the meaning of the "acid (anhydride)", "\8230; acid (anhydride)" includes both acid and anhydride thereof. In the present invention, the "acrylic resin" refers to a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylate having a carboxyl group.
In the present invention, the term "monomer" is a term that is opposite to a so-called high molecular substance (polymer), and includes a dimer, a trimer, an oligomer, and the like in addition to a monomer (monomer) in a narrow sense.
In the present invention, the "total solid content" refers to all components other than the solvent contained in the photosensitive coloring composition or the ink described later.
In the present invention, "weight average molecular weight" means a weight average molecular weight (Mw) measured by GPC (gel permeation chromatography) and converted to polystyrene.
In the present invention, unless otherwise specified, the "amine number" represents an amine number converted into an effective solid content, and is a value expressed by the equivalent KOH mass as an amount of base per 1g of solid content of the dispersant. The measurement method will be described later. On the other hand, unless otherwise specified, the "acid value" means an acid value converted into an effective solid content, and is calculated by neutralization titration.
In addition, with respect to pigments, "c.i." means the pigment index number.
In the present specification, the percentage and the part by mass are the same as the percentage and the part by weight.
[ photosensitive coloring composition ]
The photosensitive coloring composition of the invention contains the following components as essential components:
(a) Colouring agent
(b) Alkali soluble resin
(c) Photopolymerization initiator
(d) Ethylenically unsaturated compounds
(e) Solvent(s)
(f) A dispersant which is a mixture of a dispersant and a surfactant,
if necessary, the composition further contains other compounding ingredients such as an adhesion improving agent such as a silane coupling agent, a coatability improving agent, a development improving agent, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative, and each compounding ingredient is usually used in a state of being dissolved or dispersed in a solvent.
In the photosensitive coloring composition of the present invention, (a) the colorant comprises: (a1) An organic black pigment comprising at least one member 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, (a 2) C.I. pigment blue 60, and (a 3) carbon black, wherein the content of the organic black pigment (a 1) is 150 parts by mass or more per 100 parts by mass of the carbon black (a 3). The components are described in detail below.
< (a) a colorant
The colorant (a) in the photosensitive coloring composition of the present invention contains the following (a 1), (a 2) and (a 3) as essential components.
(a1) An organic black pigment comprising at least one member 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
(a2) C.i. pigment blue 60
(a3) Carbon black
Of these pigments, (a 1) and (a 2) are organic pigments, and (a 3) is an inorganic pigment.
< (a 1) organic black pigment
As described above, the colorant (a) contained in the photosensitive coloring composition of the present invention contains (a 1) an organic black pigment (hereinafter, may be abbreviated as "(a 1) organic black pigment") 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 as an essential component. By containing the (a 1) organic black pigment, it is considered that the light-shielding property can be secured, the decrease in the voltage holding ratio of the liquid crystal can be suppressed, and the shape and the level difference can be easily controlled by suppressing the absorption of ultraviolet rays.
[ chemical formula 2]
Figure BDA0002123220590000071
In the formula (I), R 1 And R 6 Each independently is a hydrogen atom, CH 3 、CF 3 Fluorine atom or chlorine atom;
R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R 10 Each independently is a hydrogen atom, a halogen atom, R 11 、COOH、COOR 11 、COO - 、CONH 2 、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH 2 、OOCNHR 11 、OOCNR 11 R 12 、NO 2 、NH 2 、NHR 11 、NR 11 R 12 、NHCOR 12 、NR 11 COR 12 、N＝CH 2 、N＝CHR 11 、N＝CR 11 R 12 、SH、SR 11 、SOR 11 、SO 2 R 11 、SO 3 R 11 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 11 Or SO 2 NR 11 R 12 ；
And is selected from R 2 And R 3 、R 3 And R 4 、R 4 And R 5 、R 7 And R 8 、R 8 And R 9 And R 9 And R 10 Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR 21 Bridging to bond each other;
R 11 and R 12 Each independently is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The compound represented by the general formula (I) and the geometric isomer of the compound have the following core structure (wherein the substituent in the structural formula is omitted), and the trans-trans isomer may be most stable.
[ chemical formula 3]
Figure BDA0002123220590000072
When the compound represented by the general formula (I) is anionic, it is preferably a salt obtained by compensating the charge of any known suitable cation, for example, a metal, organic, inorganic or metal organic cation, specifically a tertiary amine such as an alkali metal, an alkaline earth metal, a transition metal, a primary amine, a secondary amine or a trialkylamine, or a quaternary ammonium or organometallic complex compound such as tetraalkylammonium. When the geometric isomer of the compound represented by the general formula (I) is anionic, the same salt is preferable.
Among the substituents of the general formula (1) and their definitions, the following substituents are preferred from the viewpoint of having a tendency to increase the shielding rate. This is because the following substituents are not absorbed and do not affect the hue of the pigment.
R 2 、R 4 、R 5 、R 7 、R 9 And R 10 Each independently is preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.
R 3 And R 8 Each independently preferably represents a hydrogen atom or 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 Alpha-naphthyl, beta-naphthyl, SO 3 H or SO 3 - More preferably a hydrogen atom or SO 3 H。
R 1 And R 6 Each independently preferably represents a hydrogen atom or CH 3 Or CF 3 More preferably a hydrogen atom.
Preferably selected from R 1 And R 6 、R 2 And R 7 、R 3 And R 8 、R 4 And R 9 And R 5 And R 10 At least one combination of (1) is composed of the same substituents, more preferably R 1 And R 6 Are the same asSubstituent of (1), R 2 And R 7 Are identical substituents, R 3 And R 8 Are identical substituents, R 4 And R 9 Are the same substituents, and R 5 And R 10 Are the same substituents.
Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a 2-methylbutyl group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2, 2-dimethylpropyl group, an n-hexyl group, a heptyl group, an n-octyl group, a 1, 3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, or a dodecyl group.
Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl cyclohexylmethyl, trimethylcyclohexyl, thujyl norbornyl, bornyl, norcarane alkyl, carane alkyl,
Figure BDA0002123220590000081
Alkyl, norpinanyl, pinanyl, 1-adamantyl or 2-adamantyl.
Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl and 2-
Figure BDA0002123220590000082
The radical-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl and 1-p-cyclonen
Figure BDA0002123220590000092
En-8-yl, 4 (10) -limonene-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norcareen-3-yl, or camphyl.
Examples of the alkynyl group having 2 to 12 carbon atoms include a 1-propyn-3-yl group, a 1-butyn-4-yl group, a 1-pentyn-5-yl group, a 2-methyl-3-butyn-2-yl group, a1, 4-pentadiyn-3-yl group, a1, 3-pentadiyn-5-yl group, a 1-hexyn-6-yl group, a cis-3-methyl-2-penten-4-yn-1-yl group, a trans-3-methyl-2-penten-4-yn-1-yl group, a1, 3-hexadiyn-5-yl group, a 1-octyn-8-yl group, a 1-nonyn-9-yl group, a 1-decyn-10-yl group and a 1-dodecyn-12-yl group.
The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The organic black pigment (a 1) may contain a plurality of compounds selected from the group consisting of the compound represented by the general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. From the viewpoint of light-shielding properties and electrical reliability, the organic black pigment (a 1) is preferably composed of at least one selected from the group consisting of the compound represented by the 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 organic black pigment (a 1) is preferably a compound represented by the following general formula (I-1) and/or a geometric isomer of the compound, and more preferably a compound represented by the following general formula (I-1).
[ chemical formula 4]
Figure BDA0002123220590000091
Specific examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably dispersed in a dispersant or a solvent by the method described later. In addition, if a sulfonic acid derivative (sulfonic acid substituent) of the compound represented by the above general formula (I), particularly a sulfonic acid derivative of the compound represented by the above general formula (I-1) is present at the time of dispersion, dispersibility and storage stability may be improved, and therefore, it is preferable that the organic black pigment (a 1) further contains these sulfonic acid derivatives. Examples of the sulfonic acid derivative includeSuch as: selected from R in the above general formula (I) 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 And R 10 At least one of them being SO 3 Sulfonic acid derivatives of H.
In addition, in order to adjust the chroma, it is preferable that the organic black pigment (a 1) further contains a compound represented by the following general formula (I-2) and/or a geometric isomer of the compound.
[ chemical formula 5]
Figure BDA0002123220590000101
< (a 2) C.I. pigment blue 60 >
The colorant (a) contained in the photosensitive coloring composition of the present invention contains (a 2) c.i. pigment blue 60 as an essential component.
The organic black pigment (a 1) has high transmittance at a wavelength of 650 to 750nm and insufficient light-shielding property in the wavelength range, but since the c.i. pigment blue 60 (a 2) has an absorption band in the wavelength range, it is considered that the transmittance in the wavelength range can be reduced by using the c.i. pigment blue 60 (a 2) in combination.
Further, with respect to other blue pigments such as c.i. pigment blue 15, the (a 2) c.i. pigment blue 60 has high transmittance in the vicinity of 300 to 400nm, and it is easy to control the shape and level difference of the coloring spacer by suppressing absorption of ultraviolet rays. In addition, the elution of impurities is small, the voltage holding ratio is high, and the ion density is low. In particular, since the absorption of ultraviolet rays is small, decomposition by ultraviolet irradiation, elution of impurities, and the like are also small, and even after ultraviolet irradiation for improving the liquid crystal alignment properties, the voltage holding ratio and the ion density are less lowered, and the electric reliability is excellent.
< (a 3) carbon Black
The colorant (a) contained in the photosensitive coloring composition of the present invention contains carbon black (a 3) as an essential component.
(a3) Since carbon black has an absorption spectrum over the entire wavelength in the visible light region and has low transmittance, it is considered that high light-shielding properties can be achieved and light leakage can be suppressed by further containing (a 3) carbon black in addition to (a 1) the organic black pigment and (a 2) the c.i. pigment blue 60, and that high electrical reliability can be ensured by reducing the content ratio of the colorant to the entire solid content.
Examples of the carbon black include the following.
Mitsubishi chemical corporation: MA7, MA8, MA11, MA77, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3750, #3950, #4000, #4010, # 7B, OIL9B, OIL11B, OIL30B, OIL31B
Manufactured by Degussa: printex (registered trademark, the same shall apply hereinafter) 3, printex3OP, printex30OP, printex40, printex45, printex55, printex60, printex75, printex80, printex85, printex90, printex A, printex L, printex G, printex P, printex U, printex V, special Black550, special Black350, special Black250, special Black100, special Black6, special Black5, special Black4, color Black FW1, color FW2V, color FW18, color Black 200, color S160, color Black S170
Manufactured by Cabot corporation: monarch (registered trademark, the same below) 120, monarch280, monarch460, monarch800, monarch880, monarch900, monarch1000, monarch1100, monarch1300, monarch1400, monarch4630, REGAL (registered trademark, the same below) 99, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PERALS 480, PERALS 130, VULCA (registered trademark, the same below) 72R, ELFTEX (registered trademark) -8
Manufactured by Birror corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, 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
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, further preferably 5 or less, and particularly preferably 4 or less. When the content is not more than the above upper limit, the dispersant tends to be easily attached and the dispersibility tends to be good. The surface pH of carbon black is preferably lower, but is usually 2 or more.
The surface pH of carbon black can be measured by the following method: carbon black powder was dispersed in water, and the aqueous pH measurement was performed on the dispersion.
The average particle diameter of the carbon black is preferably 8nm or more, more preferably 17nm or more, further preferably 21nm or more, and preferably 100nm or less, more preferably 65nm or less, further preferably 40nm or less, particularly preferably 32nm or less. When the amount is equal to or less than the upper limit, dispersion stability and storage stability tend to be good, and when the amount is equal to or more than the lower limit, light-shielding properties tend to be good.
The average particle diameter of the carbon black in the present invention is an index average particle diameter. Generally, images are taken at several tens of thousands times by electron microscope observation, photographs are taken for several visual fields, about 2000 to 3000 particles are measured on these photographs by an image processing apparatus, and the average particle diameter of carbon black is determined by particle image analysis.
Carbon black coated with a resin may be used as the carbon black. When carbon black coated with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. As the carbon black coated with a resin, for example, carbon black described in japanese patent application laid-open No. h 09-71733 can be preferably used. In view of volume resistance and dielectric constant, resin-coated carbon black is preferably used.
As the carbon black to be subjected to the coating treatment with the resin, the total content of Na and Ca is preferably 100ppm or less. Carbon black generally contains ash components such as Na, ca, K, mg, al, and Fe mixed from raw oil, fuel oil (or gas), reaction termination water, and granulation water during production, and furnace materials of a reactor. Among them, na and Ca are usually contained in an amount of several hundred ppm or more, and the decrease in Na and Ca suppresses penetration into the transparent electrode (ITO) and other electrodes, thereby tending to prevent electrical short circuits.
As a method for reducing the content of these ashes containing Na and Ca, a method of strictly selecting materials with extremely low Na and Ca contents as feedstock oil, fuel oil (or gas), and reaction terminating water in the production of carbon black, and a method of extremely reducing the amount of alkali materials for adjusting the structure can be adopted. Other methods include a method of washing carbon black produced from a furnace with water, hydrochloric acid, or the like to dissolve and remove Na and Ca.
Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide water, and then a solvent that is hardly soluble in water is added, the carbon black is transferred to the solvent side, and is completely separated from water, and almost all of Na and Ca present in the carbon black are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100ppm or less, it may be possible to achieve only a carbon black production process in which the raw materials are strictly selected alone or a method in which the raw materials are dissolved in water or acid alone, but it is easier to reduce the total amount of Na and Ca to 100ppm or less by using both methods in combination.
The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. The dispersion diameter (agglomerate size) in water is preferably small, and the coating under fine cells can be performed. More preferably, carbon black having an average particle diameter of 40nm or less and a dibutyl phthalate (DBP) absorption of 140ml/100g or less. When the amount is within the above range, a coating film having good light-shielding properties tends to be obtained.
The method for producing the resin-coated carbon black is not particularly limited, and for example, after the blending amounts of the carbon black and the resin are appropriately adjusted, the following method can be employed:
1. mixing a resin with a solvent such as cyclohexanone, toluene, xylene, etc., heating and dissolving the mixture to prepare a resin solution, mixing carbon black and water to prepare a suspension, mixing and stirring the resin solution and the suspension to separate the carbon black from the water, removing the water, heating and kneading the mixture to obtain a composition, forming the obtained composition into a sheet, pulverizing the sheet, and drying the sheet;
2. mixing and stirring the resin solution and the suspension prepared in the same manner as described above, granulating the carbon black and the resin, separating the obtained granules, heating, and removing the residual solvent and water;
3. dissolving carboxylic acid such as maleic acid and fumaric acid in the solvent exemplified above, adding carbon black, mixing, drying, removing the solvent to obtain carbon black to which carboxylic acid is attached (added), and then adding resin thereto and dry-mixing;
4. stirring the monomer component containing reactive group and water which form the resin to be coated at high speed to prepare suspension, cooling after polymerization, obtaining the resin containing reactive group from the polymer suspension, adding carbon black into the suspension, mixing, reacting the carbon black with the reactive group (grafting the carbon black), cooling and crushing; and so on.
The type of resin to be coated is also not particularly limited, and is usually a synthetic resin, and a resin further having a benzene ring core in the structure is preferable from the viewpoint of the same action, dispersibility and dispersion stability as the amphoteric surfactant.
Specific examples of the synthetic resin include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphosate resin, epoxy resin, and alkylbenzene resin, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfone, polyphenylsulfone, polyarylate, and polyether ether ketone. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the amount of the coating resin is not less than the lower limit, the carbon black can be sufficiently coated. On the other hand, when the amount is equal to or less than the upper limit, the adhesion between the resins tends to be prevented and the dispersibility tends to be good.
The carbon black coated with the resin in this way can be used as a colorant for forming a colored spacer by a usual method, and a color filter having the colored spacer as a constituent can be produced by a usual method. When such carbon black is used, a colored spacer having a high light-shielding rate and a low surface reflectance tends to be realized at low cost. Further, coating the surface of carbon black with a resin is also expected to have an effect of encapsulating Na and Ca in carbon black.
< other colorants >
The colorant (a) contained in the photosensitive coloring composition of the present invention may contain other colorants such as other pigments and other dyes in addition to the pigments (a 1), (a 2) and (a 3). The color of the other colorant is not particularly limited, and colorants of respective colors such as red, orange, blue, violet, green, and yellow can be used. In addition, black pigments other than the above (a 1) and (a 3) may be used. As the other colorant, an organic pigment is preferably used from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal, suppressing absorption of ultraviolet rays, and easily controlling the shape and height difference of the colored spacer.
The chemical structure of the other pigments is not particularly limited, except for azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, bisindolinone
Figure BDA0002123220590000141
Organic pigments such as oxazines, indanthrene and perylene, and various inorganic pigments can be used. Specific examples of pigments that can be used in the present invention are shown below by the pigment numbers.
As a red pigment, there can be cited c.i. pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48. Among them, from the viewpoint of light-shielding properties and dispersibility, c.i. pigment red 48. When the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a red pigment having a low ultraviolet absorption rate as the red pigment, and from such a viewpoint, c.i. pigment red 254 and 272 are more preferably used.
Examples of orange (orange) pigments include c.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. pigment orange 13, 43, 64, 72 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet light, an orange pigment having a low ultraviolet light absorption rate is preferably used as the orange pigment, and from this viewpoint, c.i. pigment orange 64, 72 is more preferred, and c.i. pigment orange 64 is even more preferred.
As a blue pigment, c.i. pigment blue 1, 2, 9, 14, 15. Among them, c.i. pigment blue 15, 16 are preferable from the viewpoints of dispersibility and light-shielding property.
As the violet pigment, c.i. pigment violet 1, 2, 3, 1, 3. Among them, from the viewpoint of light-shielding properties, c.i. pigment violet 19, 23, 29 is preferably used, and c.i. pigment violet 23, 29 is more preferably used.
In addition, c.i. pigment violet 23, 29 is preferably used from the viewpoint of dispersibility and light-shielding properties, and in the case where the photosensitive coloring composition is cured by ultraviolet light, a violet pigment having a low ultraviolet light absorption rate is preferably used as the violet pigment, and from this viewpoint, c.i. pigment violet 29 is more preferred. In addition, c.i. pigment violet 29 is also preferable from the viewpoint of light-shielding properties.
Examples of the organic coloring pigment that can be used other than the red pigment, the orange pigment, the blue pigment, and the violet pigment include a green pigment and a yellow pigment.
Examples of the green pigment include c.i. pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, and 55. Among them, c.i. pigment green 7 and 36 are preferably listed.
As the yellow pigment, there can be cited c.i. pigment yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 1, 36. Among them, from the viewpoint of dispersibility and reliability, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150, and 180 are more preferable.
Among these, an orange pigment and/or a violet pigment is preferable from the viewpoint of light-shielding properties and reliability, and a violet pigment is more preferable from the viewpoint of light-shielding properties, and c.i. pigment violet 29 is further more preferable.
Examples of black pigments other than (a 1) and (a 3) include acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and the like.
Further, as the other dyes, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like can be exemplified.
As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black 5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, etc.
Examples of the anthraquinone dyes include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.
Examples of the phthalocyanine dyes include c.i. vat blue 5, quinonimine dyes include c.i. basic blue 3 and c.i. basic blue 9, quinoline dyes include c.i. solvent yellow 33, c.i. acid yellow 3 and c.i. disperse yellow 64, and examples of the nitro dyes include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
The above (a 1), (a 2), (a 3) and other pigments are preferably used in such a manner that they are dispersed so that their average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the average particle diameter is based on the number of pigment particles.
The average particle diameter of the pigment is a value determined from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on the photosensitive coloring composition after being sufficiently diluted (usually diluted to prepare a pigment concentration of about 0.005 to 0.2 mass%, but according to the recommended concentration of the pigment by a measuring instrument), and the measurement is performed at 25 ℃.
Alkali soluble resin (b)
The alkali-soluble resin (b) used in the present invention is not particularly limited as long as it contains a carboxyl group or a hydroxyl group, and examples thereof include: epoxy (meth) acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak resins, polyvinyl phenol resins, and the like, and among them, from the viewpoint of excellent platemaking properties, it is preferable to use:
(b1) Epoxy (meth) acrylate resin
(b2) An acrylic copolymer resin, which is a copolymer resin of acrylic acid,
these may be used singly or in combination.
< (b 1) epoxy (meth) acrylate resin
(b1) The epoxy (meth) acrylate resin is obtained by reacting a hydroxyl group formed by a reaction product of an epoxy compound (epoxy resin) and an α, β -unsaturated monocarboxylic acid ester having a carboxyl group in the α, β -unsaturated monocarboxylic acid ester moiety, with a compound having 2 or more substituents capable of reacting with the hydroxyl group, such as a polybasic acid and/or an acid anhydride thereof.
Further, the (b 1) epoxy (meth) acrylate resin is also included in the resin obtained by reacting a compound having 2 or more substituents capable of reacting with a hydroxyl group before the reaction of the polybasic acid and/or its anhydride with the hydroxyl group, and then reacting the compound with the polybasic acid and/or its anhydride.
In addition, a resin obtained by further reacting a compound having a reactive functional group with a carboxyl group of the resin obtained by the above reaction is also included in the above (b 1) epoxy (meth) acrylate resin.
Therefore, epoxy (meth) acrylate resins are not limited to "(meth) acrylate" because they have substantially no epoxy group in their chemical structure, but they are conventionally named because epoxy compounds (epoxy resins) are used as raw materials and "(meth) acrylate" is a typical example thereof.
As the epoxy (meth) acrylate resin (b 1) used in the present invention, the following epoxy (meth) acrylate resin (b 1-1) and/or epoxy (meth) acrylate resin (b 1-2) (hereinafter, sometimes referred to as "carboxyl group-containing epoxy (meth) acrylate resin") are particularly preferably used from the viewpoint of developability and reliability.
< epoxy (meth) acrylate resin (b 1-1) >
An alkali-soluble resin obtained by adding an alpha, beta-unsaturated monocarboxylic acid or an alpha, beta-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and then reacting the resulting product with a polybasic acid and/or an acid anhydride thereof.
< epoxy (meth) acrylate resin alkali-soluble resin (b 1-2) >)
An alkali-soluble resin obtained by adding an alpha, beta-unsaturated monocarboxylic acid or an alpha, beta-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and then reacting the resulting product with a polyhydric alcohol and a polybasic acid and/or an acid anhydride thereof.
The epoxy resin is a material including a raw material compound before forming a resin by thermosetting, and can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenol compound with epichlorohydrin may be used. The phenol compound is preferably a compound having a phenolic hydroxyl group at a valence of 2 or more, and may be a monomer or a polymer.
As the kind of the raw material epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, triphenol methane type epoxy resin, biphenol novolac type epoxy resin, naphthalene novolac type epoxy resin, epoxy resin which is a reaction product of addition polymerization reaction of dicyclopentadiene with phenol or cresol and further with epichlorohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin, and the like can be preferably used, and epoxy resins having an aromatic ring in the main chain in this way can be suitably used.
Specific examples of the epoxy resin include bisphenol A type epoxy resins (e.g., "JeR (registered trademark, the same shall apply hereinafter)" 828", JP 1001", JP 1002", JP 1004", manufactured by Mitsubishi chemical corporation), epoxy resins obtained by reacting epichlorohydrin with alcoholic hydroxyl groups of bisphenol A type epoxy resins (e.g., "NER-1302" (epoxy equivalent 323, softening point 76 ℃ manufactured by Mitsubishi chemical corporation), bisphenol F type resins (e.g., "Epikote 807", "EP-4001", "EP-4002", "EP-4004", manufactured by Mitsubishi chemical corporation), epoxy resins obtained by reacting epichlorohydrin with alcoholic hydroxyl groups of bisphenol F type epoxy resins (e.g., "NER-EO06" (epoxy equivalent 350, softening point 66 ℃ manufactured by Mitsubishi chemical corporation), bisphenol S type epoxy resins, biphenyl glycidyl ethers (e.g., "YX-4000", manufactured by Mitsubishi chemical corporation), "phenol novolac (e.g.," epoxy equivalent 74N-EOH 06 "(epoxy equivalent 350, softening point 66 ℃ manufactured by Mitsubishi chemical corporation)," PIX-4000 ", manufactured by Mitsubishi chemical corporation)," PIX-O epoxy novolak 32 ", manufactured by Mitsubishi chemical corporation", and "PIC 102", manufactured by Mitsubishi chemical corporation), epoxy novolak 32 ", and" PIC 102 ", manufactured by Mitsubishi chemical corporation", epoxy novolak 32 ", manufactured by Mitsubishi chemical corporation, and" PIC 32 ", manufactured by Mitsubishi chemical corporation", and "manufactured by Mitsubishi chemical corporation", epoxy novolak 32 ", and so on 102", and the same as epoxy novolak resin, manufactured by Mitsubishi chemical corporation ", and the same as epoxy novolak resin, manufactured by Mitsubishi chemical corporation, trisphenolmethane type epoxy resins (for example, "EPPN (registered trademark, hereinafter the same)") -501"," EPN-502"," EPPN-503", manufactured by japan chemical company), alicyclic epoxy resins (for example," Celloxide (registered trademark, hereinafter the same) "2021P", and "Celloxide EHPE", manufactured by xylonite chemical industry co., inc.), epoxy resins obtained by glycidating a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example, "EXA-7200", manufactured by DIC corporation, "NC-7300", manufactured by japan chemical company), epoxy resins represented by the following general formulae (B1) to (B4), and the like. Specifically, the epoxy resin may be represented by the following general formula (B1) "XD-1000" manufactured by Nippon chemical Co., ltd., the following general formula (B2) "NC-3000" manufactured by Nippon chemical Co., ltd., the following general formula (B2) "ESF-300" manufactured by Nippon Tekkon chemical Co., ltd., the following general formula (B4) "ESF-300", and the like.
[ chemical formula 6]
Figure BDA0002123220590000191
In the general formula (B1), a represents an average value and represents a number of 0 to 10, and R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R present in 1 molecule 111 May be the same or different.
[ chemical formula 7]
Figure BDA0002123220590000192
In the general formula (B2), B represents an average value and represents a number of 0 to 10, and R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R present in 1 molecule 121 May be the same or different.
[ chemical formula 8]
Figure BDA0002123220590000193
In the general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2), wherein the molecular structure contains 1 or more adamantane structures, and c represents an integer of 2 or 3.
[ chemical formula 9]
Figure BDA0002123220590000201
In the above general formulae (B3-1) and (B3-2), R 131 ～R 134 And R 135 ～R 137 Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent, and represents a bonding site.
[ chemical formula 10]
Figure BDA0002123220590000202
In the general formula (B4), p and q each independently represent an integer of 0 to 4, and R 141 And R 142 Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R 143 And R 144 Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represent an integer of 0 or more.
Among these, the epoxy resin represented by any one of the general formulae (B1) to (B4) is preferably used.
As the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, examples thereof include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-or p-vinylbenzoic acid, a halogenated alkyl group at the α -position of (meth) acrylic acid, an alkoxy group, a halogen atom, a nitro group, and a cyano-substituted compound, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalic adipic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhexanoic adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylhutylhydrophthalic acid, 2- (meth) acryloyloxybutylhutylhutylhydrophthalic acid, 2- (meth) acryloyloxybutylhydrolactone, 2- (meth) butyrolactone, 2- (meth) acryloyloxybutylhydrolactone, butyrolactone, delta-lactone, and the like, pentaerythritol tri (meth) acrylate, and an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride), or maleic acid (anhydride) added thereto, and (meth) acrylic acid dimers.
Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group may be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150 ℃. Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride.
The epoxy resin, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of 2 or more.
The α, β -unsaturated monocarboxylic acid or α, β -unsaturated monocarboxylic acid ester having a carboxyl group is used in the following amounts: the epoxy resin preferably has an epoxy group content of 1 equivalent, in the range of 0.5 to 1.2 equivalents, and more preferably 0.7 to 1.1 equivalents. When the amount of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group is not less than the above lower limit, the shortage of the amount of the unsaturated group introduced can be suppressed, and the subsequent reaction with the polybasic acid and/or the anhydride thereof tends to be sufficient. On the other hand, when the amount is not more than the above upper limit, the amount of the unreacted product of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed from remaining, and the curing properties tend to be improved easily.
Examples of the polybasic acid and/or the acid anhydride thereof include one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalate, endomethylenetetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and acid anhydrides of these acids.
Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid or anhydrides of these acids are preferred. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride.
The addition reaction of the polybasic acid and/or the acid anhydride thereof can be carried out by a known method under the same conditions as the addition reaction of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin to obtain the target product. The amount of the polybasic acid and/or the acid anhydride component thereof added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150mg KOH/g, more preferably in the range of 20 to 140mg KOH/g. When the amount of addition of the polybasic acid and/or the acid anhydride component thereof is equal to or more than the lower limit, the alkali developability tends to be good, and when the amount of addition of the polybasic acid and/or the acid anhydride component thereof is equal to or less than the upper limit, the curability tends to be good.
In addition reaction of the polybasic acid and/or the acid anhydride thereof, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, pentaerythritol, dipentaerythritol, or the like may be added to introduce a multi-branched structure.
The carboxyl group-containing epoxy (meth) acrylate-based resin is generally obtained as follows: the heating is performed after mixing the polybasic acid and/or the anhydride thereof with the reactant of the epoxy resin and the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, or after mixing the polybasic acid and/or the anhydride thereof and the polyfunctional alcohol with the reactant of the epoxy resin and the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group. In this case, the mixing order of the polybasic acid and/or anhydride thereof and the polyfunctional alcohol is not particularly limited. By heating, the polybasic acid and/or its anhydride and any hydroxyl group present in the mixture of the reactant of the epoxy resin and the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol undergo an addition reaction.
As the epoxy (meth) acrylate resin, in addition to the above, there can be mentioned epoxy (meth) acrylate resins described in Korean patent laid-open publication No. 10-2013-0022955, and the like.
The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, more preferably 7000 or less. When the lower limit value is set to be equal to or higher than the lower limit value, the solubility in the developer tends to be suppressed from becoming excessively high, and when the upper limit value is set to be equal to or lower than the upper limit value, the solubility in the developer tends to be easily improved. For example, 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, further preferably 3000 to 8000, particularly preferably 4000 to 8000, and most preferably 5000 to 7000.
The acid value of the epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, and further preferably 50mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less, and particularly preferably 100mgKOH/g or less. When the lower limit value is not less than the above lower limit value, appropriate developing solubility tends to be obtained, and when the upper limit value is not more than the above upper limit value, film dissolution tends to be suppressed without excessive development. For example, the combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 150mgKOH/g, still more preferably 40 to 100mgKOH/g, and particularly preferably 50 to 100mgKOH/g.
The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, and from the viewpoint of developability and reliability, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b 1-I) (hereinafter, may be abbreviated as "(b 1-I) epoxy (meth) acrylate resin") and/or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (b 1-II) (hereinafter, may be abbreviated as "(b 1-II) epoxy (meth) acrylate resin") is preferably contained.
[ chemical formula 11]
Figure BDA0002123220590000231
In the formula (b 1-I), R 11 Represents a hydrogen atom or a methyl group, R 12 Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in the formula (b 1-I) may be further substituted with an arbitrary substituent.
[ chemical formula 12]
Figure BDA0002123220590000232
In the formula (b 1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 And R 16 Each independently represents a 2-valent aliphatic group optionally having a substituent, m and n each independently represent an integer of 0 to 2, and x represents a bonding position.
(b 1-I) epoxy (meth) acrylate resin
First, the epoxy (meth) acrylate resin having a partial structure represented by the above general formula (b 1-I) will be described in detail.
[ chemical formula 13]
Figure BDA0002123220590000241
In the formula (b 1-I), R 11 Represents a hydrogen atom or a methyl group, R 12 Represents a 2-valent hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in the formula (b 1-I) may be further substituted with an arbitrary substituent.
(R 12 )
In the above formula (b 1-I), R 12 Represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group, a 2-valent aromatic ring group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film during development tend to be suppressed, and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
Specific examples of the 2-valent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include those having a structure having a side chain of, among the aforementioned linear aliphatic groups having a valence of 2, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or the like.
The number of rings having a cyclic aliphatic group having a valence of 2 is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is formed, and the substrate adhesion tends to be good, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film during development tend to be easily suppressed, and image resolution tends to be improved. Specific examples of the 2-valent cyclic aliphatic group include those obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, or dicyclopentadiene. Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring.Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring with 2 free valences perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002123220590000251
A ring, a benzophenanthrene ring, an acenaphthene ring, an anthryl ring, a fluorene ring, etc.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Figure BDA0002123220590000252
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxaz->
Figure BDA0002123220590000253
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a/or a/V group>
Figure BDA0002123220590000254
A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc.
Of these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally having a 2-valent aromatic ring group 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, from the viewpoint of developing solubility, the compound is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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 the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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.
Specific examples of the group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups are linked include groups represented by the following formulae (b 1-I-A) to (b 1-I-F). Among these groups, the group represented by the following formula (b 1-I-A) is preferable from the viewpoint of rigidity of the skeleton and hydrophobization of the film.
[ chemical formula 14]
Figure BDA0002123220590000271
As described above, the benzene ring in the formula (b 1-I) may be further substituted with an optional substituent. Examples of the substituent 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 the substituents is also not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable.
In addition, the partial structure represented by the above formula (b 1-I) is preferably a partial structure represented by the following formula (b 1-I-1) from the viewpoint of ease of synthesis.
[ chemical formula 15]
Figure BDA0002123220590000281
In the formula (b 1-I-1), R 11 And R 12 R has the same meaning as in the above formula (b 1-I) X Represents a hydrogen atom or a polybasic acid residue, and represents a bonding position. The benzene ring in the formula (b 1-I-1) may be further substituted with an arbitrary substituent.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. The polybasic acid may be one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethenyltetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
The partial structure represented by the above formula (b 1-I-1) contained in 1 molecule of the (b 1-I) epoxy (meth) acrylate resin may be one or 2 or more, and for example, R may be present in combination X Is a hydrogen atom and R X Is a polybasic acid residue.
The number of partial structures represented by the above formula (b 1-I) contained in 1 molecule of the (b 1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15.
The weight average molecular weight (Mw) of the (b 1-I) epoxy (meth) acrylate resin in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, still further preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and is preferably 30000 or less, more preferably 20000 or less, further preferably 10000 or less, particularly preferably 8000 or less. When the lower limit value is not less than the lower limit value, the residual film ratio of the photosensitive coloring composition tends to be good, and when the upper limit value is not more than the upper limit value, the resolution tends to be good. For example, the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 2000 to 10000, further preferably 3000 to 10000, particularly preferably 4000 to 80000, and most preferably 5000 to 8000.
The acid value of the (b 1-I) epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, further preferably 50mgKOH/g or more, particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 130mgKOH/g or less, particularly preferably 100mgKOH/g or less. When the lower limit value is not less than the above lower limit value, the developing solubility tends to be improved and the resolution tends to be good, and when the upper limit value is not more than the above upper limit value, the residual film ratio of the photosensitive coloring composition tends to be good. For example, the combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 150mgKOH/g, still more preferably 40 to 100mgKOH/g, yet more preferably 50 to 100mgKOH/g, and particularly preferably 80 to 100mgKOH/g.
Specific examples of the (b 1-I) epoxy (meth) acrylate resin are shown below. In the examples, a symbol indicates a bonding position.
[ chemical formula 16]
Figure BDA0002123220590000291
[ chemical formula 17]
Figure BDA0002123220590000301
[ chemical formula 18]
Figure BDA0002123220590000302
[ chemical formula 19]
Figure BDA0002123220590000303
(b 1-II) epoxy (meth) acrylate resin
Next, the epoxy (meth) acrylate resin having a partial structure represented by the above general formula (b 1-II) will be described in detail.
[ chemical formula 20]
Figure BDA0002123220590000304
In the formula (b 1-II), R 13 Each independently represents a hydrogen atom or a methyl group, R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 And R 16 Each independently represents an optionally substituted 2-valent aliphatic group, and m and n eachIndependently represents an integer of 0 to 2, and represents a bonding position.
(R 14 )
In the above general formula (b 1-II), R 14 Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings included in the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, 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 aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, and further preferably 8 to 20.
Specific examples of the alicyclic ring in the alicyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isonicotinic ring, an adamantane ring, and a cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the colored photosensitive composition.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 3 or more, and is usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is not easily generated, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, 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.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. When the lower limit is not less than the above-described lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-described upper limit, patterning characteristics tend to be good. For example, 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.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002123220590000321
A ring, a benzophenanthrene ring, an acenaphthylene ring, a fluoranthene ring, a fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.
In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched and cyclic groups. Among these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, the combination of the upper limit and the lower limit is preferably 1 to 25, more preferably 3 to 20, and further preferably 6 to 15.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and adhesion to a substrate tends to be good, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity, reduction of the film during development, and improvement of resolution tend to be easily suppressed. For example, 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.
Specific examples of the 2-valent cyclic aliphatic group include groups obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
Examples of the substituent optionally contained in the 2-valent aliphatic group 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; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the 2-valent aromatic ring group include a 2-valent aromatic ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring with 2 free valences perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0002123220590000331
A ring, a benzophenanthrene ring, an acenaphthene ring, an anthryl ring, a fluorene ring, etc.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of 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 having 2 free valences,
Figure BDA0002123220590000332
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furo-pyrrole ringFuran ring, thienofuran ring, benzisoxaz->
Figure BDA0002123220590000333
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a/or a/V group>
Figure BDA0002123220590000334
A pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Of these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
As the substituent optionally having a 2-valent aromatic ring group, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and the like are mentioned. Among these, from the viewpoint of developing solubility, the compound is preferably unsubstituted.
Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic ring groups are linked.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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 the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, 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.
Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the above formulae (b 1-I-A) to (b 1-I-F). Among these, the group represented by the above formula (b 1-I-C) is preferable from the viewpoint of rigidity of the skeleton and hydrophobization of the film.
The bonding mode of the cyclic hydrocarbon group as the side chain of these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the side chain is substituted for 1 hydrogen atom of an aliphatic group or an aromatic ring group, or a cyclic hydrocarbon group having 1 carbon atom of an aliphatic group as a side chain.
(R 15 、R 16 )
In the above general formula (b 1-II), R 15 And R 16 Each independently represents a 2-valent aliphatic group optionally having a substituent.
Examples of the 2-valent aliphatic group include linear, branched and cyclic groups. Among these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, further preferably 10 or less. When the lower limit value is equal to or higher than the above-described lower limit value, a strong film is easily obtained, surface roughness is less likely to occur, and adhesion to a substrate tends to be good. For example, the combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and further preferably 6 to 10.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Specific examples of the 2-valent branched aliphatic group include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 12 or less, preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and adhesion to a substrate tends to be good, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity, reduction of the film during development, and improvement of resolution tend to be easily suppressed. For example, the combination of the upper limit and the lower limit is preferably 1 to 12, more preferably 2 to 10.
Specific examples of the 2-valent cyclic aliphatic group include groups obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, or dicyclopentadiene. Among these, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
(m、n)
In the general formula (b 1-II), m and n each independently represent an integer of 0 to 2. When the lower limit value is set to the upper limit value or more, the patterning property tends to be good and surface roughness tends not to be generated, and when the upper limit value is set to the lower limit value or less, the developing property tends to be good. From the viewpoint of developability, m and n are preferably 0, and from the viewpoint of patterning suitability and surface roughness, m and n are preferably 1 or more.
In addition, the partial structure represented by the general formula (b 1-II) is preferably a partial structure represented by the following general formula (b 1-II-1) from the viewpoint of adhesion to a substrate.
[ chemical formula 21]
Figure BDA0002123220590000361
In the formula (b 1-II-1), R 13 、R 15 、R 16 M and n are as defined above for formula (b 1-II), R α Represents an optionally substituted 1-valent cyclic hydrocarbon group, p is an integer of 1 or more, and represents a bonding position. The benzene ring in the formula (b 1-II-1) is optionally further substituted with an optional substituent.
(R α )
In the above general formula (b 1-II-1), R α Represents a 1-valent cyclic hydrocarbon group optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the lower limit is not less than the above-described lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-described upper limit, patterning characteristics tend to be good. For example, 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 aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit is not less than the above-described lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-described upper limit, patterning characteristics tend to be good. For example, 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 8 to 15.
Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit is not less than the above-described lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-described upper limit, patterning characteristics tend to be good. For example, 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.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, further preferably 15 or less. When the lower limit is not less than the above-described lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-described upper limit, patterning characteristics tend to be good. For example, 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.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, and the like. Among these, the fluorene ring is preferable from the viewpoint of developing solubility.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the above-mentioned lower limit value, the film curing degree and the residual film ratio tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the developing property tends to be good. For example, the combination of the upper limit and the lower limit is preferably 1 to 3, and more preferably 2 to 3.
Of these, R is from the viewpoint of a strong film curing degree α Preferably a 1-valent aliphatic ring group, more preferably an adamantyl group.
As described above, the benzene ring in the formula (b 1-II-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is also not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, the non-substitution is preferable.
Specific examples of the partial structure represented by the above formula (b 1-II-1) are shown below.
[ chemical formula 22]
Figure BDA0002123220590000371
[ chemical formula 23]
Figure BDA0002123220590000381
[ chemical formula 24]
Figure BDA0002123220590000382
[ chemical formula 25]
Figure BDA0002123220590000383
[ chemical formula 26]
Figure BDA0002123220590000384
/>
From the viewpoint of rigidity of the skeleton and hydrophobization of the film, the partial structure represented by the general formula (b 1-II) is preferably a partial structure represented by the following general formula (b 1-II-2).
[ chemical formula 27]
Figure BDA0002123220590000385
In the formula (b 1-II-2), R 13 、R 15 、R 16 M and n are as defined above for formula (b 1-II), R β Represents a 2-valent cyclic hydrocarbon group optionally having a substituent, and represents a bonding position. The benzene ring in the formula (b 1-II-2) is optionally further substituted with an optional substituent.
(R β )
In the above formula (b 1-II-2), R β Represents a 2-valent cyclic hydrocarbon group optionally having a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the lower limit value is set to be equal to or higher than the lower limit value, film roughness during development tends to be suppressed, and when the upper limit value is set to be equal to or lower than the lower limit value, deterioration of sensitivity and reduction of film during development tend to be suppressed, and resolution tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and further preferably 8 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of film reduction and resolution at the time of development.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, 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.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, particularly preferably 15 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, 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.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, and the like. Among these, the fluorene ring is preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Among these, R is from the viewpoint of suppressing film reduction and resolution β Preferably a 2-valent aliphatic ring group, more preferably a 2-valent adamantyl ring group.
On the other hand, from the viewpoint of patterning characteristics, R β Preferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in the formula (b 1-II-2) may be further substituted with an arbitrary substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1, or 2 or more.
In addition, 2 benzene rings may be linked together via a substituent. As the substituent in this case, there may be mentioned, mention may be made of-O-, -S- ] -NH-, -CH 2 -an equivalent 2-valent group.
Among these, from the viewpoint of patterning characteristics, the non-substitution is preferable. In addition, methyl substitution is preferable from the viewpoint of less tendency to cause film reduction or the like.
Specific examples of the partial structure represented by the above formula (b 1-II-2) are listed below, and in the examples, the bonding site is indicated.
[ chemical formula 28]
Figure BDA0002123220590000401
[ chemical formula 29]
Figure BDA0002123220590000411
[ chemical formula 30]
Figure BDA0002123220590000412
[ chemical formula 31]
Figure BDA0002123220590000413
On the other hand, the partial structure represented by the above formula (b 1-II) is preferably a partial structure represented by the following formula (b 1-II-3) from the viewpoint of the residual film ratio of the coating film and the patterning property.
[ chemical formula 32]
Figure BDA0002123220590000414
In the formula (b 1-II-3), R 13 、R 14 、R 15 、R 16 M and n are as defined above for formula (b 1-II), R Z Represents a hydrogen atom or a polybasic acid residue.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. It is noted that 1 OH group may be further removed from the molecule and R in the other molecule represented by the formula (b 1-II-3) Z Common, i.e. can be through R Z A plurality of the formulae (b 1-II-3) are linked.
The polybasic acid may be one or 2 or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethenyltetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
The partial structure represented by the above formula (b 1-II-3) contained in 1 molecule of the (b 1-II) epoxy (meth) acrylate resin may be one type, or 2 or more types, and for example, R may be present in combination Z Is a hydrogen atom and R Z Is a polybasic acid residue.
The number of partial structures represented by the above formula (b 1-II) contained in 1 molecule of the (b 1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is not more than the above-described upper limit value, deterioration of sensitivity and reduction of the film at the time of development are easily suppressed, and resolution tends to be improved. For example, 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) of the (b 1-II) epoxy (meth) acrylate resin in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, and is preferably 30000 or less, more preferably 20000 or less, further preferably 10000 or less, further preferably 7000 or less, and particularly preferably 5000 or less. When the lower limit value is not less than the above-mentioned lower limit value, patterning characteristics tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur. For example, the combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1000 to 20000, further preferably 2000 to 10000, further preferably 2000 to 7000, and particularly preferably 2000 to 5000.
The acid value of the (b 1-II) epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, further preferably 60mgKOH/g or more, particularly preferably 80mgKOH/g or more, most preferably 100mgKOH/g or more, and preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less. When the lower limit value is not less than the above lower limit value, a strong film tends to be easily obtained, and when the upper limit value is not more than the above upper limit value, the developing solubility tends to be improved and the resolution tends to be good. For example, the combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 150mgKOH/g, still more preferably 40 to 150mgKOH/g, yet more preferably 60 to 120mgKOH/g, and particularly preferably 80 to 120mgKOH/g.
The epoxy (meth) acrylate resin may be used alone or in combination with 2 or more kinds of resins.
In addition, a part of the epoxy (meth) acrylate resin described above may be replaced with another binder resin. That is, the epoxy (meth) acrylate resin may be used in combination with another binder resin. In this case, 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, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less.
For example, the combination of the upper limit and the lower limit is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.
The other binder resin that can be used in combination with the epoxy (meth) acrylate-based resin is not particularly limited as long as it is selected from resins generally used for photosensitive coloring compositions. Examples of the binder resin include those described in Japanese patent application laid-open Nos. 2007-271727, 2007-316620, and 2007-334290. The other binder resins may be used alone or in combination of 2 or more.
In addition, as the alkali-soluble resin (b), from the viewpoint of compatibility with a pigment, a dispersant, and the like, (b 2) an acrylic copolymer resin is preferably used, and those described in japanese patent application laid-open No. 2014-137466 can be preferably used.
Examples of the acrylic copolymer resin include copolymers of an ethylenically unsaturated monomer having 1 or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b 2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b 2-2)").
Examples of the unsaturated monomer (b 2-1) include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, and mesaconic acid; mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as mono [ 2- (meth) acryloyloxyethyl ] succinate and mono [ 2- (meth) acryloyloxyethyl ] phthalate; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone mono (meth) acrylate; p-vinylbenzoic acid, and the like.
These unsaturated monomers (b 2-1) may be used alone or in admixture of 2 or more.
Examples of the unsaturated monomer (b 2-2) include:
n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;
methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate Alkenoic acid ester, polyethylene glycol (degree of polymerization 2-10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ](meth) acrylates such as decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of p-cumylphenol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl ] oxetane, and 3- [ (meth) acryloyloxymethyl ] -3-ethyloxetane;
cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ]Vinyl ethers such as decan-8-yl vinyl ether, pentacyclopentadecyl vinyl ether and 3- (vinyloxymethyl) -3-ethyloxetane;
and macromonomers having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b 2-2) may be used alone or in admixture of 2 or more.
In the copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2), the copolymerization ratio of the unsaturated monomer (b 2-1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b 2-1) in such a range, a photosensitive coloring composition having excellent alkali developability and storage stability tends to be obtained.
Specific examples of the copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2) include copolymers disclosed in, for example, japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118, and 2004-101728.
The copolymer of the unsaturated monomer (b 2-1) and the unsaturated monomer (b 2-2) can be produced by a known method, and the structure, mw and Mw/Mn can be controlled by the methods disclosed in, for example, japanese patent application laid-open No. 2003-222717, japanese patent application laid-open No. 2006-259680, international publication No. 2007/029871 and the like.
< (c) photopolymerization initiator
(c) The photopolymerization initiator is a component that directly absorbs light to cause a decomposition reaction or a hydrogen abstraction reaction, and has a function of generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added.
Examples of the photopolymerization initiator include metallocene compounds containing a titanocene compound as described in, for example, japanese patent application laid-open Nos. 59-152396 and 61-151197; hexaarylbiimidazole derivatives described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent laid-open publication No. 10-39503
Figure BDA0002123220590000451
Oxadiazole derivatives, halomethyl s-triazine derivatives; an alpha-aminoalkylphenone derivative; and oxime ester derivatives described in, for example, japanese patent application laid-open Nos. 2000-80068 and 2006-36750.
Specifically, for example, as the titanocene derivatives, there can be mentioned: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2, 3,4,5, 6-pentafluoro-1-yl) titanium, dicyclopentadienyl bis (2, 3,5, 6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2, 4, 6-trifluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2, 6-difluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl-1-yl) titanium, dicyclopentadienyl [2, 6-difluoro-3- (prop-1-yl) -phenyl-1-yl ] titanium and the like.
Further, examples of the hexaarylbiimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole 2-mer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole 2-mer, (4' -methoxyphenyl) -4, 5-diphenylimidazole 2-mer, etc.
In addition, as halomethylation
Figure BDA0002123220590000452
Oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4- & ltwbr/& gton->
Figure BDA0002123220590000453
Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-/>
Figure BDA0002123220590000454
Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-/>
Figure BDA0002123220590000455
Diazole, 2-trichloromethyl-5-furyl-1, 3,4- & ltwbr & gt>
Figure BDA0002123220590000456
Oxadiazoles, and the like.
Further, examples of the halomethyl-s-triazine derivatives 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.
Further, as α -aminoalkylphenone derivatives, there can be mentioned: 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-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, and the like.
The oxime ester compounds are effective as photopolymerization initiators particularly in terms of sensitivity and platemaking property, and the oxime ester compounds having excellent sensitivity are particularly useful when an alkali-soluble resin containing a phenolic hydroxyl group is used. Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in the structure, the sensitivity is high even in a small amount and the reaction to heat is stable, and a photosensitive coloring composition having high sensitivity can be obtained in a small amount.
Examples of the oxime ester compounds include compounds represented by the following general formula (IV).
[ chemical formula 33]
Figure BDA0002123220590000461
In the above formula (IV), R 21a Represents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent, R 21b Represents an optional substituent comprising an aromatic ring or a heteroaromatic ring, R 22a Represents an alkanoyl group optionally having a substituent, or an aroyl group optionally having a substituent.
R 21a The number of carbon atoms of the alkyl group in (b) 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. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group. For example, 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.
Examples of the substituent optionally contained in the alkyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group, an N-acetyl-N-acetoxyamino group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
As R 21a As the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, and is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. For example, 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.
Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like, and among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent optionally contained in the aromatic ring group 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 to each other.
Among these, R is R from the viewpoint of developability 21a Preferred is an aromatic ring group optionally having a substituent, and more preferred is an aromatic ring group having an alkoxy group bonded to a substituent.
In addition, as R 21b Preferred are optionally substituted carbazolyl groups, optionally substituted thioxanthone groups or optionally substituted diphenylsulfide groups. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity. On the other hand, from the viewpoint of electrical reliability, an optionally substituted diphenylsulfide group is preferable.
In addition, R 22a The number of carbon atoms of the alkanoyl group in (b) 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 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. For example, 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 acetyl, propionyl, and butyryl.
Examples of the substituent optionally contained in the alkanoyl group include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group and the like, and the substituent is preferably unsubstituted from the viewpoint of ease of synthesis.
In addition, R 22a The number of carbon atoms of the aroyl group in (2) 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 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the aroyl group include benzoyl group and naphthoyl group. For example, the combination of the upper limit and the lower limit is preferably 7 to 20, more preferably 8 to 15, and further preferably 8 to 10.
Examples of the substituent optionally contained in the aroyl group include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, and the like, and from the viewpoint of ease of synthesis, the substituent is preferably unsubstituted.
Of these, R is from the viewpoint of sensitivity 22a Preferred is an alkanoyl group optionally having a substituent, more preferred is an unsubstituted alkanoyl group, and further preferred is an acetyl group.
The photopolymerization initiator may be used alone or in combination of 2 or more.
In order to improve the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended as necessary in the photopolymerization initiator. Examples of the sensitizing dye include: japanese patent laid-open Nos. 4-221958 and 4-219756
Figure BDA0002123220590000481
Xanthene dye, coumarin dye having a heterocyclic ring as described in Japanese patent laid-open Nos. 3-239703 and 5-289335, 3-oxocoumarin compound as described in Japanese patent laid-open Nos. 3-239703 and 5-289335, methylenepyrrole dye as described in Japanese patent laid-open No. 6-19240, and Japanese patent laid-open Nos. 47-2528 and 54-155292,And pigments having a dialkylaminobenzene skeleton described in Japanese patent publication No. 45-37377, japanese patent publication No. 48-84183, japanese patent publication No. 52-112681, japanese patent publication No. 58-15503, japanese patent publication No. 60-88005, japanese patent publication No. 59-56403, japanese patent publication No. 2-69, japanese patent publication No. 57-168088, japanese patent publication No. 5-107761, japanese patent publication No. 5-210240, and Japanese patent publication No. 4-288818.
Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are benzophenone-based compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzo
Figure BDA0002123220590000482
Azole, 2- (p-diethylaminophenyl) benzo->
Figure BDA0002123220590000483
Azole, 2- (p-dimethylaminophenyl) benzo [4,5]Benzo->
Figure BDA0002123220590000484
Azole, 2- (p-dimethylaminophenyl) benzo [6,7]Benzo->
Figure BDA0002123220590000485
Azole, 2, 5-bis (p-diethylaminophenyl) -1,3,4- & ltwbr/& gt>
Figure BDA0002123220590000486
Oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridineAnd p-dialkylaminophenyl-containing compounds such as (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Among them, the most preferable is 4,4' -dialkylaminobenzophenone.
The sensitizing dye may be used alone or in combination of 2 or more.
Examples of the polymerization accelerator 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. The polymerization accelerator may be used alone or in combination of 2 or more.
< (d) an ethylenically unsaturated compound
The photosensitive coloring composition of the present invention comprises (d) an ethylenically unsaturated compound. By including (d) an ethylenically unsaturated compound, the sensitivity is improved.
The ethylenically unsaturated compound used in the present invention is a compound having at least 1 ethylenically unsaturated group in the molecule. Specific examples thereof include (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, and monoesters of carboxylic acids having 1 ethylenically unsaturated bond and polyhydric alcohols or monohydric alcohols.
In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated groups in 1 molecule. The number of ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, and is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less. When the lower limit value is not less than the above-mentioned lower limit value, the sensitivity tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the solubility in a solvent tends to be improved. For example, 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.
As examples of polyfunctional olefinic monomers, mention may be made, for example, of: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of unsaturated carboxylic acids and polycarboxylic acids with a polyol such as an aliphatic polyol or an aromatic polyol.
Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include acrylic acid esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic acid esters obtained by replacing acrylic acid esters of these exemplified compounds with methacrylic acid esters, itaconic acid esters similarly obtained by replacing acrylic acid esters, crotonic acid esters obtained by replacing crotonic acid esters, and maleic acid esters obtained by replacing maleic acid esters.
Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and 1,2, 3-benzenetrisacrylate.
The ester obtained by esterification of a polyvalent carboxylic acid and an unsaturated carboxylic acid with a polyhydric compound is not necessarily a single substance, and representative specific examples thereof include condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; a condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerol, and the like.
Further, as examples of the polyfunctional ethylenic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ninghamu chemical Co., ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyowa Kagaku Co., ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Kagaku Co., ltd.), and the like.
Among these, from the viewpoint of curability, the ethylenically unsaturated compound (d) is preferably an alkyl (meth) acrylate, and more preferably dipentaerythritol hexaacrylate.
These may be used alone or in combination of 2 or more.
(e) solvent
The photosensitive coloring composition of the present invention comprises (e) a solvent. By containing the (e) solvent, the (a) colorant can be dissolved or dispersed in the solvent, and coating becomes easy.
The photosensitive coloring composition of the present invention is generally used in a state in which (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and other various materials used as needed are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.
Among the organic solvents, from the viewpoint of coatability, a solvent having a boiling point in the range of 100 to 300 ℃ is preferably selected, and a solvent having a boiling point in the range of 120 to 280 ℃ is more preferably selected. The boiling point referred to herein means a boiling point at a pressure of 1013.25 hPa.
Examples of such an organic solvent include the following solvents.
Glycol monoalkyl ethers such as 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 tert-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, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
Glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexyl acetate;
ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
ketones such as 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, and methoxymethyl amyl ketone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexane;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
linear or cyclic esters such as amyl 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 decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile.
Examples of the commercially available organic solvent corresponding to the above-mentioned solvent include: mineral spirits (Mineral spirits), varsol #2, apco #18solvent, apco trinner, sonal solvent nos. 1 and 2, solvesso #150, shell TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, and the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all of which are trade names of the above), and the like.
These organic solvents may be used alone, or 2 or more kinds may be used in combination.
When the colored spacer is formed by photolithography, it is preferable to select an organic solvent having a boiling point in the range of 100 to 200 ℃. More preferably an organic solvent having a boiling point of 120 to 170 ℃.
Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like, and high solubility of the constituent components in the composition.
In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. The organic solvent used in combination is particularly preferably a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is preferred in particular from the viewpoint of solubility of the constituent components in the composition. The glycol monoalkylethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate easily and the storage stability of the colored resin composition obtained thereafter tends to be lowered, for example, the viscosity increases, and therefore the proportion of the glycol monoalkylethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
In addition, it is also preferably used in combination with an organic solvent having a boiling point of 150 ℃ or higher (hereinafter, sometimes referred to as "high-boiling solvent"). When the pigment is used in combination with such a high boiling point solvent, the photosensitive coloring composition is difficult to dry, but the pigment is prevented from being broken in a uniform dispersion state in the composition in the case of rapid drying. That is, for example, the effect of preventing the occurrence of foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a colorant or the like is obtained. Among the various solvents, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol mono-ethyl ether acetate are particularly preferable from the viewpoint of high effects.
When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. When the lower limit value is not less than the above-described lower limit value, for example, the generation of a foreign matter defect at the tip of the slit nozzle due to precipitation and solidification of a color material or the like tends to be suppressed, and when the upper limit value is not more than the above-described upper limit value, the drying rate of the composition is suppressed from being lowered, and thus problems such as a tact failure in the reduced pressure drying process and pin marks in the prebaking (pre-cake) tend to be suppressed.
The high boiling point solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
Preferred high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin among the above solvents.
(f) dispersant
In the photosensitive coloring composition of the present invention, (f) a dispersant is contained because it is important to finely disperse the colorant (a) and stabilize the dispersed state thereof in order to ensure quality stability.
The dispersant (f) is preferably a polymer dispersant having a functional group, and further preferably a carboxyl group in view of dispersion stability; a phosphate group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a polymer dispersant derived from a functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. Among these, in particular, the pigment having a primary amino group, a secondary amino group or a tertiary amino group is particularly preferable from the viewpoint that the pigment can be dispersed with a small amount of a dispersant when dispersed; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine.
Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising a macromonomer and an amino group-containing monomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
Specific examples of such a dispersant include EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), disparlon (registered trademark, manufactured by Nako chemical industries, ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by shin-Etsu chemical industries, ltd.), polyflow (manufactured by Kyoho chemical Co., ltd.), ajisper (registered trademark, manufactured by K.K.).
These polymeric dispersants may be used alone or in combination of 2 or more.
The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1000 or more, and usually 100000 or less, preferably 50000 or less. For example, the combination of the upper limit and the lower limit is preferably 700 to 100000, more preferably 1000 to 50000.
Among these, from the viewpoint of pigment dispersibility, the dispersant (f) preferably contains a urethane-based polymer dispersant having a functional group and/or an acrylic-based polymer dispersant, and particularly preferably contains an acrylic-based polymer dispersant.
In addition, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferable.
Examples of the urethane and acrylic polymer dispersants include DISPERBYK160 to 166, 182 series (both of urethane), DISPERBYK2000, 2001, LPN21116 and the like (both of acrylic) (all of which are manufactured by BYK-Chemie).
Specifically, the preferable chemical structure of the urethane polymer dispersant is exemplified by a dispersion resin having a weight average molecular weight of 1000 to 200000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the molecule. The dispersion resin may be treated with a quaternizing agent such as benzyl chloride to convert all or part of the tertiary amino groups into quaternary ammonium salt groups.
Examples of the polyisocyanate compounds include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and ω, ω ' -diisocyanate dimethylcyclohexane, xylylene diisocyanate, and α, triisocyanates such as aliphatic diisocyanate having an aromatic ring, e.g., α ', α ' -tetramethylxylylene diisocyanate, lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate and triphenylthiophosphate triisocyanates, and trimers, hydrides and polyol adducts thereof. As the polyisocyanate, a trimer of an organic diisocyanate is preferable, and a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate are most preferable. These can be used alone in 1 kind, also can combine more than 2 kinds to use.
Examples of the method for producing an isocyanate trimer include the following methods: the polyisocyanate is partially trimerized with an isocyanate group using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired polyisocyanate containing a trimerized isocyanate group.
Examples of the compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like, and those obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of 2 or more of these compounds.
The polyether diol includes polyether diol, polyether ester diol, and a mixture of 2 or more of these diols. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing an alkylene oxide, for example, polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and a mixture of 2 or more thereof. Examples of the polyether ester diol include those obtained by reacting a diol having an ether group or a mixture thereof with another diol with a dicarboxylic acid or an acid anhydride thereof, or by reacting an alkylene oxide with a polyester diol, for example, poly (polyoxybutylene) adipate.
As the polyether glycol, polyethylene glycol, polypropylene glycol, polyoxybutylene 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 is most preferable.
As the polyester diol, there may be mentioned: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof with diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, bis (hydroxymethyl) cyclohexanediol, bis (hydroxymethyl) benzene, etc.) to obtain alicyclic benzene diols, etc., such as polyethylene glycol adipate, polybutylene adipate, 1, 6-hexanediol adipate, polyethylene glycol propylene glycol adipate, and the like, or polylactone diols or polylactone monools obtained by using the above diols or monools having 1 to 25 carbon atoms as an initiator, for example polycaprolactone diol, polymethylvalerolactone, and a mixture of 2 or more thereof. The polyester diol is most preferably polycaprolactone diol or polycaprolactone obtained using an alcohol having 1 to 25 carbon atoms as an initiator.
The polycarbonate diol includes, for example, poly (1, 6-hexanediol) carbonate and poly (3-methyl-1, 5-pentanediol) carbonate, and the polyolefin diol includes, for example, polybutadiene diol, hydrogenated polybutadiene diol and hydrogenated polyisoprene diol.
These can be used alone, also can be combined with 2 or more.
The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is usually
300 to 10000, preferably 500 to 6000, more preferably 1000 to 4000.
The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described.
The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, nitrogen atom or sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a mercapto group, and among them, a hydrogen atom of an amino group, particularly a primary amino group, is preferable.
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, a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having active hydrogen and tertiary amino group in the same molecule include N, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, N-dipropyl-1, 3-propanediamine, N-dibutyl-1, 3-propanediamine, N, N-dimethylethylenediamine, N-diethylethylenediamine, N-dipropylethylenediamine, N-dibutylethylenediamine, N, N-dimethyl-1, 4-butanediamine, N-diethyl-1, 4-butanediamine, N-dipropyl-1, 4-butanediamine, N-dibutyl-1, 4-butanediamine, etc.
In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring,Tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzo
Figure BDA0002123220590000561
Nitrogen-containing 5-membered heterocycles such as an azole ring, a benzothiazole ring and a benzothiadiazole ring, and nitrogen-containing 6-membered heterocycles such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring and an isoquinoline ring. Among these nitrogen-containing heterocycles, preferred is an imidazole ring or a triazole ring.
Specific examples of the compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole. Further, specific examples of these compounds having a triazole ring and an amino group include 3-amino-1, 2, 4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1, 2, 4-triazole, 4-amino-4H-1, 2, 4-triazole-3, 5-diol, 3-amino-5-phenyl-1H-1, 3, 4-triazole, 5-amino-1, 4-diphenyl-1, 2, 3-triazole, and 3-amino-1-benzyl-1H-2, 4-triazole. Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole and 3-amino-1, 2, 4-triazole are preferable.
These may be used alone or in combination of 2 or more.
The preferable blending ratio of the raw materials for producing the urethane polymer dispersant is as follows: the amount of the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the same molecule, is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, based on 100 parts by mass of the polyisocyanate compound.
The urethane polymer dispersant is produced by a known method for producing a polyurethane resin. As the solvent in the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate, and the like; hydrocarbons such as benzene, toluene, xylene, and hexane; partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tert-butyl alcohol, and chlorinated substances such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide. These may be used alone or in combination of 2 or more.
In the above production, a urethane reaction catalyst is generally used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octylate, iron-based catalysts such as iron acetylacetonate and iron chloride, and tertiary amines such as triethylamine and triethylenediamine. These may be used alone or in combination of 2 or more.
The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled so that the amine value after the reaction is in the range of 1 to 100mgKOH/g, more preferably 5 to 95 mgKOH/g. The amine number is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the amine value is less than the above range, the dispersibility tends to be lowered, and when the amine value exceeds the above range, the developability tends to be lowered.
In the case where an isocyanate group remains in the polymer dispersant in the above reaction, it is preferable that the product has high stability with time if the isocyanate group is further destroyed by an alcohol or an amino compound.
The weight average molecular weight (Mw) of the urethane polymer dispersant is usually 1000 to 200000, preferably 2000 to 100000, and more preferably 3000 to 50000. When the content is not less than the lower limit, dispersibility and dispersion stability tend to be improved, and when the content is not more than the upper limit, solubility tends to be improved and dispersibility tends to be improved.
On the other hand, as the acrylic polymer dispersant, a random copolymer, a graft copolymer, or a block copolymer of a monomer having a functional group (the functional group mentioned here is the functional group mentioned above as the functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group and containing an unsaturated group is preferably used. These copolymers can be produced by a known method.
Examples of the monomer having a functional group and containing an unsaturated group include unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or a quaternary ammonium group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternary products thereof. These may be used alone or in combination of 2 or more.
Examples of the monomer having no functional group and containing an unsaturated group include macromonomers such as 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, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and derivatives thereof, α -methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and other N-substituted maleimides, acrylonitrile, vinyl acetate and poly (meth) methyl acrylate macromonomers, polystyrene macromonomers, poly (meth) 2-hydroxyethyl acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and the like. These may be used alone or in combination of 2 or more.
The acrylic polymer dispersant is particularly preferably an ase:Sub>A-B or B-ase:Sub>A-B block copolymer composed of an ase:Sub>A block having ase:Sub>A functional group and ase:Sub>A B block having no functional group, and in this case, the ase:Sub>A block may contain ase:Sub>A partial structure derived from the monomer not having ase:Sub>A functional group but having an unsaturated group in addition to the partial structure derived from the monomer having ase:Sub>A functional group and having an unsaturated group, and these structures may be contained in the ase:Sub>A block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the a block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
The B block includes a partial structure derived from the above-mentioned monomer having no functional group but having an unsaturated group, and 1B block may contain a partial structure derived from 2 or more kinds of monomers, and these structures may be contained in the B block in any form of random copolymerization or block copolymerization.
The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below.
The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method, wherein the polymerization living species of the anionic living polymerization method is an anion, and is represented by, for example, the following synthetic route.
[ chemical formula 34]
Figure BDA0002123220590000591
In the above synthetic scheme, ar 1 Is a 1-valent organic radical, ar 2 Is different from Ar 1 M is a metal atom, and s and t are each an integer of 1 or more.
The polymerization active species of the radical active polymerization method is a radical, and is represented by, for example, the following synthetic route.
[ chemical formula 35]
Figure BDA0002123220590000601
In the above synthetic scheme, ar 1 Is a 1-valent organic radical, ar 2 Is different from Ar 1 J and k are each an integer of 1 or more, R a Is a hydrogen atom or a 1-valent organic radical, R b And R a And, instead, is a hydrogen atom or a 1-valent organic group.
For the synthesis of the acrylic polymer dispersant, publicly known methods described in Japanese patent laid-open publication No. H9-62002, P.Lutz, P.Masson et al, polymer.Bull.12, 79 (1984), B.C.Anderson, G.D.Andrews et al, macromolecules,14,1601 (1981), K.Hatada, K.Ute, et al, polym.J.17,977 (1985), 18,1037 (1986), right-handed Haoyi, panti-Tokukan, 36,366, tomura, zubenyokuguan, polymer literature, 46, 189 (1989), M.Kuroki, T.Aida, J.Am.Chem.sic,109,4737 (1987), zhantiansu, jingxiangping, ouhuanping, organic synthetic chemistry, 43,300 (1985), D.Y.Soxh.R, hercules et al, machil 3, 1987, machil et al, published by Korea.
The acrylic polymer dispersant usable in the present invention may be an ase:Sub>A-B block copolymer or ase:Sub>A B-ase:Sub>A-B block copolymer, and the ratio of the ase:Sub>A block to the B block constituting the copolymer is preferably 1/99 to 80/20, particularly preferably 5/95 to 60/40 (mass ratio), and when the ratio is within this range, the balance between dispersibility and storage stability tends to be secured.
In addition, in 1g of the A-B block copolymer and the B-A-B block copolymer which can be used in the present invention, the amount of the quaternary ammonium salt group is preferably 0.1 to 10mmol in general, and when the amount is in this range, good dispersibility tends to be ensured.
In such a block copolymer, an amino group generated in the production process may be contained, and the amine value thereof is about 1 to 100mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less. For example, the combination of the upper limit and the lower limit is preferably 10 to 90mgKOH/g, more preferably 30 to 80mgKOH/g, and still more preferably 50 to 75mgKOH/g.
Here, the amine value of the dispersant such as the block copolymer is represented by a KOH mass corresponding to the amount of base corresponding to 1g of the 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 90mgKOH/g, more preferably 30 to 80mgKOH/g, and still more preferably 50 to 75mgKOH/g.
0.5 to 1.5g of a dispersant sample was precisely weighed in a 100mL beaker, dissolved in 50mL of acetic acid, and subjected to 0.1mol/L HClO using an automatic titrator equipped with a pH electrode 4 The solution was subjected to neutralization titration with acetic acid solution, and the amine value was determined by the following equation, with the inflection point of the titration pH curve being set as the titration end point.
Amine value [ mgKOH/g ] = (561 XV)/(W.times.S)
[ wherein, W: the weighed amounts of the dispersant samples [ g ], V: the titration amount [ mL ] at the end of titration, S: the solid content concentration [ mass% ] of the dispersant sample is shown. ]
The amine value of the block copolymer depends on the presence or absence of an acid group which is the base of the acid value and the type thereof, and is usually preferably a lower acid value, usually 10mgKOH/g or less, and the weight average molecular weight (Mw) is preferably in the range of 1000 to 100000. When the amount is within the above range, good dispersibility tends to be ensured.
When the acrylic polymer dispersant has a quaternary ammonium salt group as a functional group, the specific structure of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the acrylic polymer dispersant preferably has a repeating unit represented by the following formula (i) (hereinafter, may be referred to as "repeating unit (i)").
[ chemical formula 36]
Figure BDA0002123220590000621
In the above formula (i), R 31 ～R 33 Each independently being a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, an aralkyl group optionally having a substituent, R 31 ～R 33 2 or more of them may be bonded to each other to form a cyclic structure, R 34 Is a hydrogen atom or a methyl group, X is a 2-valent linking group, Y - Are counter anions.
R of the above formula (i) 31 ～R 33 In which carbon atom of alkyl group optionally having substituent(s)The number of subunits is not particularly limited, and is usually 1 or more, and preferably 10 or less, and more preferably 6 or less. The combination of the upper limit and the lower limit is preferably 1 to 10, 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, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
R of the above formula (i) 31 ～R 33 The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. 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, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
R of the above formula (i) 31 ～R 33 The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. The combination of the upper limit and the lower limit is preferably 7 to 16, 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, and among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group are preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
Of these, R is preferable from the viewpoint of dispersibility 31 ～R 33 Each independently is alkyl or aralkyl, particularly, R is preferred 31 And R 33 Each independently is methyl or ethyl, and R 32 Is phenylmethyl or phenylethyl, more preferably R 31 And R 33 Is methyl, and R 32 Is a phenylmethyl group.
In addition, when the acrylic polymer dispersant has a tertiary amine as a functional group, it preferably has a repeating unit represented by the following formula (ii) (hereinafter, may be referred to as "repeating unit (ii)") from the viewpoint of dispersibility.
[ chemical formula 37]
Figure BDA0002123220590000631
In the above formula (ii), R 35 And R 36 Each independently being a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent, R 35 And R 36 May be bonded to each other to form a ring structure, R 37 Is a hydrogen atom or a methyl group, and Z is a linking group having a valence of 2.
R in the above formula (ii) 35 And R 36 Wherein the alkyl group optionally having a substituent(s) may be preferably used as R in the above formula (i) 31 ～R 33 But are exemplary groups.
Similarly, R is represented by the above formula (ii) 35 And R 36 Wherein the aryl group optionally having a substituent(s) may be preferably used as R in the above formula (i) 31 ～R 33 But are exemplary groups. R in the above formula (ii) 35 And R 36 As the aralkyl group optionally having a substituent(s) in (1), R of the above-mentioned formula (i) can be preferably employed 31 ～R 33 But are exemplary groups.
Of these, R 35 And R 36 Preferably each independently an optionally substituted alkyl group, more preferably a methyl or ethyl group.
R as the above formula (i) 31 ～R 33 And R of the above formula (ii) 35 And R 36 Examples of the substituent optionally contained in the alkyl group, aralkyl group or aryl group in (1) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.
In the above formulae (i) and (ii), examples of the 2-valent linking groups X and Z include: alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R 43 -radical, -COOR 44 A group [ wherein, R 43 And R 44 Is a single bond, an alkylene group having 1 to 10 carbon atoms or an ether group (an alkyloxyalkyl group) having 2 to 10 carbon atoms]Etc., preferably-COO-R 44 -a radical.
In the formula (i), Y is a counter anion - Examples thereof include Cl - 、Br - 、I - 、ClO 4 - 、BF 4 - 、CH 3 COO - 、PF 6 - And the like.
The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 35 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more, relative to the total of the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii). For example, the combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, further preferably 20 to 40 mol%, and particularly preferably 30 to 40 mol%.
The content 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, more preferably 5 mol% or more, further preferably 10 mol% or more, and preferably 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 15 mol% or less, from the viewpoint of dispersibility. For example, the combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, further preferably 10 to 20 mol%, and particularly preferably 10 to 15 mol%.
The content of the repeating unit represented by the above formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 25 mol% or less, from the viewpoint of dispersibility. For example, the combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, further preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.
In addition, from the viewpoint of improving compatibility with a binder component such as a solvent and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, may be referred to as "repeating unit (iii)").
[ chemical formula 38]
Figure BDA0002123220590000651
In the above formula (iii), R 40 Is ethylene or propylene; r 41 Is an alkyl group optionally having a substituent, R 42 Is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.
R of the above formula (iii) 41 The number of carbon atoms of the alkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. For example, 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, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
In addition, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. For example, the combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
The content of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be achieved at the same time. For example, the combination of the upper limit and the lower limit is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%.
In addition, from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability, the polymeric dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter, may be referred to as "repeating unit (iv)").
[ chemical formula 39]
Figure BDA0002123220590000661
In the above formula (iv), R 38 Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent, R 39 Is a hydrogen atom or a methyl group.
R of the above formula (iv) 38 The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((b) is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. For example, 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, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.
R of the above formula (iv) 38 The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and further 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, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.
R of the above formula (iv) 38 The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (b) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, further preferably 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 phenylmethylene, a phenylethylene, a phenylpropylene, a phenylbutylene, and a phenylisopropylene, and among these, a phenylmethylene, a phenylethylene, a phenylpropylene, and a phenylbutylene are preferable, and a phenylmethylene or a phenylethylene are more preferable.
Among these, R is from the viewpoint of solvent compatibility and dispersion stability 38 Preferably an alkyl or aralkyl group, more preferably a methyl, ethyl or phenylmethylene group.
As R 38 Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. In addition, as aryl or aralkyl radicals optionallyExamples of the substituent include a chain alkyl group, a halogen atom, and an alkoxy group. In addition, R 38 The chain alkyl group includes both straight-chain and branched-chain alkyl groups.
From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. For example, the combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more 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). Examples of such a repeating unit include styrene-based monomers derived from styrene, α -methylstyrene, and the like; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of monomers such as N-methacryloylmorpholine.
From the viewpoint of further improving the dispersibility, the polymeric dispersant is preferably a block copolymer having an a block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and no repeating unit (ii). The block copolymer is preferably an A-B block copolymer or ase:Sub>A B-A-B block copolymer. By introducing a quaternary ammonium salt group and a tertiary amino group into the a block, the dispersing ability of the dispersant tends to be remarkably improved. In addition, the B block preferably has the repeating unit (iii), and further preferably has the repeating unit (iv).
The a block may contain the repeating unit (i) and the repeating unit (ii) in any form of random copolymerization or block copolymerization. In addition, 1 a block may contain 2 or more kinds of the repeating unit (i) and the repeating unit (ii), and in this case, the a block may contain each repeating unit in any form of random copolymerization or block copolymerization.
The a block may contain a repeating unit other than the repeating unit (i) and the repeating unit (ii), and examples of such a repeating unit include a repeating unit derived from the above-mentioned (meth) acrylate 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%, and most preferably the a block does not contain the repeating unit.
The B block may contain a repeating unit other than the repeating units (iii) and (iv), and examples of such a repeating unit include styrene-based monomers derived from styrene, α -methylstyrene, and the like; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of monomers such as N-methacryloyl morpholine. 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%, and most preferably the B block does not contain the repeating unit.
In addition, from the viewpoint of improving dispersion stability, (f) a dispersant is preferably used in combination with a pigment derivative described later.
< other compounding ingredients of photosensitive coloring composition >
In addition to the above components, additives such as adhesion improving agents such as silane coupling agents, surfactants (coating property improving agents), pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, development improving agents, ultraviolet absorbers, and antioxidants can be suitably blended in the photosensitive coloring composition of the present invention.
(1) Adhesion improver
In order to improve adhesion to a substrate, an adhesion enhancer may be contained in the photosensitive coloring composition of the present invention. The adhesion improver is preferably a silane coupling agent, a compound containing a phosphoric group, or the like.
The silane coupling agent may be 1 kind of epoxy, meth (acrylic), or amino silane coupling agent, or 2 or more kinds of silane coupling agents may be used alone or in combination.
Preferred silane coupling agents include, for example: (meth) acryloyloxysilanes such as 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane, epoxysilanes such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane and isocyanatosilanes such as 3-isocyanatopropyltriethoxysilane, and particularly preferred are silane coupling agents of the epoxysilanes type.
The phosphoric acid group-containing compound is preferably a (meth) acryloyl group-containing phosphate ester, and more preferably a compound represented by the following general formula (g 1), (g 2) or (g 3).
[ chemical formula 40]
Figure BDA0002123220590000691
In the above general formulae (g 1), (g 2) and (g 3), R 51 Represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.
These phosphoric acid group-containing compounds may be used alone or in combination of 2 or more.
(2) Surface active agent
In order to improve coatability, a surfactant may be contained in the photosensitive coloring composition of the present invention.
As the surfactant, various surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Among them, nonionic surfactants are preferably used in view of low possibility of exerting adverse effects on various properties, and among them, fluorine-based and silicone-based surfactants are effective in view of coatability.
Examples of such surfactants include: TSF4460 (manufactured by Momentive Performance Materials Co., ltd.), DFX-18 (manufactured by NEOS Co., ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie Co., ltd.), KP340 (manufactured by shin-Etsu Silicone Co., ltd.), F-470, F-475, F-478, F-559 (manufactured by DIC Co., ltd.), SH7PA (manufactured by Toray Silicone Co., ltd.), DS-401 (manufactured by Dajindo Co., ltd.), L-77 (manufactured by Union corporation, japan), FC4430 (manufactured by 3M Co., ltd.), and the like.
One kind of surfactant may be used, or 2 or more kinds may be used in combination in any combination and ratio.
(3) Pigment derivatives
The photosensitive coloring composition of the present invention may further contain a pigment derivative as a dispersion aid for improving dispersibility and storage stability.
Examples of the pigment derivative include azo compounds, phthalocyanine compounds, quinacridone compounds, benzimidazolone compounds, quinophthalone compounds, isoindolinone compounds, and bisquinophthalone compounds
Figure BDA0002123220590000692
Azines, anthraquinones, indanthrene, perylene, perinone, diketopyrrolopyrroles, di->
Figure BDA0002123220590000701
Of the oxazine derivatives, phthalocyanines and quinophthalones are preferred.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, and the like, and these groups may be bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, and the like. In addition, a plurality of these substituents may be substituted on one pigment skeleton.
Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, and bis Sulfonic acid derivatives of ketopyrrolopyrroles, bis
Figure BDA0002123220590000702
Sulfonic acid derivatives of oxazines, and the like. These pigment derivatives may be used singly or in combination of 2 or more.
(4) Photoacid generators
The photo-acid generator is a compound capable of generating an acid by ultraviolet rays, and the photo-acid generator allows a crosslinking reaction to proceed in the presence of a crosslinking agent such as a melamine compound by the action of the acid generated during exposure. Among such photoacid generators, those having high solubility in solvents, particularly solvents used for photosensitive coloring compositions, are preferred, and examples thereof include: diphenyl iodide
Figure BDA0002123220590000703
Dimethyl phenyl iodine->
Figure BDA00021232205900007013
Phenyl (p-methoxybenzyl) iodine->
Figure BDA00021232205900007014
Bis (m-nitrophenyl) iodo>
Figure BDA00021232205900007015
Bis (p-tert-butylphenyl) iodo->
Figure BDA00021232205900007016
Bis (p-chlorophenyl) iodo>
Figure BDA00021232205900007017
Double (n-dodecyl) iodine->
Figure BDA00021232205900007018
P-isobutylphenyl (p-tolyl) iodide->
Figure BDA00021232205900007019
P-isopropylphenyl (p-toluene)Base) iodine->
Figure BDA00021232205900007011
Isodiaryliodine->
Figure BDA00021232205900007020
And triarylsulfonium chlorides, bromides, borofluorides such as triphenylsulfonium, hexafluorophosphate, hexafluoroarsenite, aromatic sulfonates, tetrakis (pentafluorophenyl) borate, sulfonium-organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, and triazine compounds such as 2-methyl-4, 6-bis (trichloromethyl) triazine and 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) triazine, but are not limited thereto.
(5) Crosslinking agent
The photosensitive coloring composition of the present invention may further contain a crosslinking agent, and for example, a melamine or guanamine compound may be used. Examples of the crosslinking agent include melamine and guanamine compounds represented by the following general formula (6).
[ chemical formula 41]
Figure BDA0002123220590000711
In the formula (6), R 61 represents-NR 66 R 67 A group or an aryl group having 6 to 12 carbon atoms, R 61 is-NR 66 R 67 In the case of radicals, R 62 、R 63 、R 64 、R 65 、R 66 And R 67 represents-CH 2 OR 68 Radical, R 61 In the case of an aryl group having 6 to 12 carbon atoms, R 62 、R 63 、R 64 And R 65 represents-CH 2 OR 68 Radical, R 62 、R 63 、R 64 、R 65 、R 66 And R 67 The remaining radicals in (A) represent, independently of one another, hydrogen or-CH 2 OR 68 Radical, R 68 Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl group and naphthyl group may have a substituent such as an alkyl group, an alkoxy group or a halogen atom bonded thereto. The alkyl group and the alkoxy group each have about 1 to 6 carbon atoms. In the above, R 68 The alkyl group is a methyl group or an ethyl group, and a methyl group is particularly preferable.
The melamine-based compounds corresponding to the general formula (6), i.e., the compounds of the following general formula (6-1), include: hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, etc.
[ chemical formula 42]
Figure BDA0002123220590000712
In the formula (6-1), R 62 、R 63 、R 64 、R 65 、R 66 And R 67 In the case that one of them is an aryl group, R 62 、R 63 、R 64 And R 65 represents-CH 2 OR 68 Radical, R 62 、R 63 、R 64 、R 65 、R 66 And R 67 The remaining groups in (a) represent, independently of each other, a hydrogen atom or-CH 2 OR 68 Radical, R 68 Represents a hydrogen atom or an alkyl group.
Guanamine compounds corresponding to the general formula (6), that is, R in the general formula (6) 61 Compounds that are aryl groups include: tetramethylolbenzoguanamine, tetramethoxymethylbenzguanamine, trimethoxymethylbenzguanamine, tetraethoxymethylbenzguanamine, and the like.
In addition, crosslinkers having methylol or methylol alkyl ether groups may also be used. Examples thereof are listed 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-ethyldimethylol triazine)Ketone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3, 5-bis (hydroxymethyl) perhydro-1, 3,5-
Figure BDA0002123220590000721
Diazin-4-one (known as dimethylol furfural) or its dimethyl ether, tetramethylol glyoxal diurea (tetramethylol glyoxal diurine) or its tetramethyl ether.
These crosslinking agents may be used alone or in combination of two or more. When the crosslinking agent is used, the amount thereof is preferably 0.1 to 15% by weight, and particularly preferably 0.5 to 10% by weight, based on the total solid content of the photosensitive coloring composition.
(6) Mercapto compounds
In addition, a mercapto compound may be added as a polymerization accelerator in order to improve adhesion to the substrate.
Examples of the mercapto compound include 2-mercaptobenzothiazole and 2-mercaptobenzo
Figure BDA0002123220590000722
Mercapto compounds having a heterocyclic ring such as oxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramer propionate, pentaerythritol tetramer acetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, and polyfunctional aliphatic compounds. These mercapto compounds may be mono One kind may be used alone, or more than 2 kinds may be mixed.
(7) Polymerization inhibitor
The photosensitive coloring composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control. It is considered that the cone angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled by containing a polymerization inhibitor which inhibits radical polymerization of the lower layer of the coating film.
As the polymerization inhibitor, there may be mentioned: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-t-butyl-4-cresol (BHT), and the like. Among these polymerization inhibitors, 2, 6-di-t-butyl-4-methylphenol is preferable from the viewpoint of shape control. In addition, hydroquinone monomethyl ether and methyl hydroquinone are preferable from the viewpoint of safety to the human body.
The polymerization inhibitor preferably contains one or more than 2 kinds. In the production of the alkali-soluble resin (b), a polymerization inhibitor may be contained in the resin, and the same or a different polymerization inhibitor may be added in addition to the polymerization inhibitor contained in the resin in the production of the photosensitive resin composition.
When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, and is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, of the total solid content of the photosensitive coloring composition. By setting the lower limit value to be equal to or higher than the lower limit value, the shape tends to be controllable, and by setting the upper limit value to be equal to or lower than the upper limit value, the necessary sensitivity tends to be maintained. For example, 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.
< content ratio of each component in photosensitive coloring composition >
In the photosensitive coloring composition of the present invention, the content of the (a) colorant is not particularly limited, and is usually 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, further preferably 30% by mass or more, particularly preferably 32% by mass or more, most preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 38% by mass or less, most preferably 35% by mass or less, in the entire solid content in the photosensitive coloring composition. When the content ratio of the colorant (a) is equal to or higher than the lower limit, sufficient light-shielding properties tend to be obtained, and when the content ratio is equal to or lower than the upper limit, sufficient plate-making characteristics tend to be easily obtained and electrical reliability tends to be excellent. For example, the combination of the upper limit and the lower limit is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, even more preferably 25 to 45% by mass, even more preferably 30 to 40% by mass, even more preferably 32 to 38% by mass, and particularly preferably 35 to 38% by mass.
(a1) The content ratio of the organic black pigment is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less, of the total solid content of the photosensitive coloring composition. When the lower limit value is set to be equal to or higher than the lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is set to be equal to or lower than the upper limit value, electrical reliability tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, even more preferably 10 to 25% by mass, and particularly preferably 15 to 20% by mass.
(a2) The content of the c.i. pigment blue 60 is not particularly limited, but is preferably 2 mass% or more, more preferably 3 mass% or more, further preferably 4 mass% or more, further preferably 6 mass% or more, particularly preferably 8 mass% or more, and most preferably 10 mass% or more, and is preferably 15 mass% or less, more preferably 12 mass% or less, further preferably 10 mass% or less, further preferably 9 mass% or less, and particularly preferably 8 mass% or less, in the entire solid content of the photosensitive coloring composition. When the lower limit value is not less than the above-mentioned lower limit value, the transmittance in the vicinity of 700nm tends to be lowered, and when the upper limit value is not more than the above-mentioned upper limit value, the electrical reliability is improved and sufficient plate making characteristics tend to be easily obtained. For example, the combination of the upper limit and the lower limit is preferably 2 to 15% by mass, more preferably 3 to 15% by mass, even more preferably 4 to 12% by mass, and particularly preferably 6 to 12% by mass.
(a3) The content ratio of the carbon black is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 4% by mass or more, and is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less, of the total solid content of the photosensitive coloring composition. When the lower limit value is not less than the above-described lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is not more than the above-described upper limit value, the transmittance in the near infrared region tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, even more preferably 3 to 8% by mass, even more preferably 4 to 7% by mass, and particularly preferably 4 to 5% by mass.
When the photosensitive coloring composition contains a violet pigment as another colorant, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, further preferably 4% by mass or more, particularly preferably 6% by mass or more, and most preferably 7% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less, of the total solid content of the photosensitive coloring composition. When the lower limit value is not less than the above-described lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is not more than the above-described upper limit value, electrical reliability tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, even more preferably 3 to 10% by mass, even more preferably 4 to 8% by mass, particularly preferably 6 to 8% by mass, and most preferably 7 to 8% by mass.
The content of the (a 1) organic black pigment with respect to the total colorant contained in the photosensitive coloring composition, that is, with respect to the (a) colorant is not particularly limited, but is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 60% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, and particularly preferably 65% by mass or less. When the lower limit value is not less than the above-mentioned lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, electrical reliability tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 20 to 80% by mass, more preferably 30 to 80% by mass, even more preferably 40 to 75% by mass, and even more preferably 50 to 70% by mass.
The content of the (a 2) c.i. pigment blue 60 with respect to the total colorant contained in the photosensitive coloring composition, that is, with respect to the (a) colorant 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, further preferably 18% by mass or more, further preferably 20% by mass or more, particularly preferably 24% by mass or more, most preferably 28% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the lower limit value is not less than the lower limit value, the transmittance in the vicinity of 700nm tends to be lowered, and when the upper limit value is not more than the upper limit value, the electrical reliability is improved, and sufficient plate making characteristics tend to be easily obtained. For example, the combination of the upper limit and the lower limit is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 18 to 40% by mass, even more preferably 24 to 35% by mass, and particularly preferably 28 to 35% by mass.
The content of the carbon black (a 3) with respect to the total colorant contained in the photosensitive coloring composition, that is, with respect to the colorant (a) 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, further preferably 18% by mass or more, particularly preferably 20% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less. When the lower limit value is not less than the above-described lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is not more than the above-described upper limit value, the transmittance in the near infrared region tends to be improved. For example, the combination of the upper limit and the lower limit is preferably 10 to 35% by mass, more preferably 12 to 30% by mass, still more preferably 15 to 25% by mass, and particularly preferably 18 to 20% by mass.
On the other hand, in order to achieve both the transmittance in the near infrared region and the electrical reliability, the content ratio of the organic black pigment (a 1) and the carbon black (a 3) in the black pigment is preferably appropriately adjusted. Since carbon black has a high absorbance in the visible region, the transmittance at a wavelength around 700nm can be effectively reduced, and the content of a colorant required for obtaining a predetermined light-shielding property tends to be reduced, thereby improving the electrical reliability. On the other hand, since carbon black also absorbs in the near infrared region, it is considered that the inclusion of a given amount of (a 1) organic black pigment in addition to (a 3) carbon black ensures sufficient light-shielding properties while ensuring transmittance at a wavelength of around 900 nm.
The content ratio of the (a 1) organic black pigment is usually 150 parts by mass or more, more preferably 180 parts by mass or more, further preferably 200 parts by mass or more, further preferably 210 parts by mass or more, still further preferably 220 parts by mass or more, still further preferably 250 parts by mass or more, still further preferably 300 parts by mass or more, still further preferably 350 parts by mass or more, still further preferably 400 parts by mass or more, particularly preferably 450 parts by mass or more, most preferably 480 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, further preferably 600 parts by mass or less, and particularly preferably 500 parts by mass or less, relative to 100 parts by mass of the (a 3) carbon black. When the lower limit value is not less than the lower limit value, the transmittance in the near infrared region tends to be improved, and when the upper limit value is not more than the upper limit value, the electrical reliability tends to be improved. For example, 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, further preferably 200 to 800 parts by mass, further preferably 210 to 600 parts by mass, further preferably 220 to 600 parts by mass, further preferably 250 to 600 parts by mass, further preferably 300 to 600 parts by mass, further preferably 350 to 600 parts by mass, further preferably 400 to 600 parts by mass, particularly preferably 450 to 500 parts by mass, and most preferably 480 to 500 parts by mass.
From the viewpoint of having both light-shielding properties and transmittance at a wavelength of about 900nm, the content ratio of the total organic pigments to the carbon black (a 3) is preferably appropriately adjusted.
The content ratio of the total organic pigments is usually 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, further preferably 600 parts by mass or more, particularly preferably 620 parts by mass or more, most preferably 650 parts by mass or more, and preferably 900 parts by mass or less, more preferably 800 parts by mass or less, relative to 100 parts by mass of the carbon black (a 3). When the lower limit value is set to the value not less than the lower limit value, the transmittance at a wavelength of about 900nm tends to be improved, and when the upper limit value is set to the value not more than the upper limit value, sufficient light shielding properties are obtained and light leakage at a wavelength of about 700nm tends to be suppressed. For example, 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, further preferably 500 to 900 parts by mass, further preferably 550 to 800 parts by mass, further preferably 600 to 800 parts by mass, particularly preferably 620 to 800 parts by mass, and most preferably 650 to 800 parts by mass.
From the viewpoint of suppressing light leakage at a wavelength of around 700nm, the content ratio of (a 2) c.i. pigment blue 60 to (a 3) carbon black is preferably appropriately adjusted.
The content ratio of the (a 2) c.i. 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, further preferably 180 parts by mass or more, further preferably 200 parts by mass or more, further preferably 210 parts by mass or more, particularly preferably 220 parts by mass or more, most preferably 240 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass or less, relative to 100 parts by mass of the (a 3) carbon black. When the lower limit value is set to the value not less than the lower limit value, light leakage at a wavelength around 700nm tends to be suppressed, and when the upper limit value is set to the value not more than the upper limit value, transmittance at a wavelength around 900nm tends to be improved. For example, 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, further preferably 200 to 300 parts by mass, particularly preferably 220 to 300 parts by mass, and most preferably 240 to 300 parts by mass.
When the photosensitive coloring composition contains a violet pigment as another colorant, it is preferable to appropriately adjust the content ratio of the violet pigment to the organic black pigment (a 1) from the viewpoint of light-shielding properties.
The content ratio of the violet 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, further preferably 55 parts by mass or more, further preferably 60 parts by mass or more, particularly preferably 65 parts by mass or more, most preferably 70 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, further preferably 80 parts by mass or less, further preferably 70 parts by mass or less, and particularly preferably 65 parts by mass or less, with respect to 100 parts by mass of the organic black pigment (a 1). When the lower limit value is set to the upper limit value or more, sufficient light shielding properties are secured, and reliability tends to be improved, and when the upper limit value is set to the lower limit value or less, light leakage at a wavelength around 700nm tends to be suppressed. For example, 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, further preferably 40 to 100 parts by mass, further preferably 55 to 100 parts by mass, further preferably 60 to 100 parts by mass, particularly preferably 65 to 90 parts by mass, and most preferably 70 to 90 parts by mass.
(b) The content ratio of the alkali-soluble resin is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and 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, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, of the total solid content of the photosensitive coloring composition of the present invention. When the content of the alkali-soluble resin (b) is not less than the lower limit, the solubility of the unexposed portion in the developer is reduced, and thus the development failure tends to be reduced. By setting the upper limit value to be equal to or lower than the above-described upper limit value, the following tendency is present: the exposure portion can be inhibited from dissolving in the developing solution while maintaining appropriate sensitivity, and the sharpness and the decrease in adhesion of the pixel can be inhibited. For example, the combination of the upper limit and the lower limit is, for example, preferably 10 to 85 mass%, more preferably 20 to 80 mass%, further preferably 30 to 70 mass%, further preferably 35 to 60 mass%, further preferably 40 to 60 mass%, and particularly preferably 40 to 50 mass%.
(b1) The content ratio of the epoxy (meth) acrylate resin is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more, and is usually 45% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. When the lower limit value is not less than the lower limit value, solubility of an unexposed portion in a developer tends to be ensured, and when the upper limit value is not more than the upper limit value, the following tendency is present: the exposure portion can be suppressed from dissolving in the developer while maintaining appropriate sensitivity, and the sharpness and adhesion of the pixel can be suppressed from lowering. For example, the combination of the upper limit and the lower limit is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 40% by mass, even more preferably 20 to 35% by mass, and particularly preferably 25 to 35% by mass.
(b) The content of the (b 1) epoxy (meth) acrylate resin contained in the alkali-soluble resin is not particularly limited, and is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more, and is usually 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less. When the lower limit value is not less than the lower limit value, solubility of an unexposed portion in a developer tends to be ensured, and when the upper limit value is not more than the upper limit value, the following tendency is present: the exposure portion can be suppressed from dissolving in the developer while maintaining appropriate sensitivity, and the sharpness and adhesion of the pixel can be suppressed from lowering. For example, 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.
(c) The content of the photopolymerization initiator is not particularly limited, and is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. When the content of the photopolymerization initiator (c) is not less than the lower limit, the sensitivity tends to be suppressed from decreasing, and when the content is not more than the upper limit, the solubility of the unexposed portion in the developer tends to be suppressed from decreasing, and the development failure tends to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, even more preferably 1 to 8% by mass, even more preferably 2 to 8% by mass, particularly preferably 3 to 8% by mass, and most preferably 4 to 7% by mass.
When the photopolymerization initiator (c) is used together with a polymerization accelerator, the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, and usually 10% by mass or less, and preferably 5% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention, and the polymerization accelerator is preferably used in a proportion of usually 0.1 to 50 parts by mass, and particularly 0.1 to 20 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (c). When the content ratio of the polymerization accelerator is set to the lower limit or more, there is a tendency that a decrease in sensitivity to exposure light can be suppressed, and when the content ratio is set to the upper limit or less, there is a tendency that a decrease in solubility of an unexposed portion in a developer can be suppressed, and thus development failure can be suppressed.
When the sensitizing dye is used in addition to the photopolymerization initiator (c), the content thereof is not particularly limited, and is usually 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less of the total solid content of the photosensitive coloring composition from the viewpoint of sensitivity.
(d) The content of the ethylenically unsaturated compound is not particularly limited, and is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, of the total solid content of the photosensitive coloring composition of the present invention. When the lower limit value is not less than the above-described lower limit value, the following tendency is present: by setting the upper limit value or less, it is possible to suppress the penetration of the developing solution into the exposed portion, and thus a favorable image tends to be obtained easily. For example, 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 still more preferably 10 to 15% by mass.
The photosensitive coloring composition of the present invention is prepared by adjusting the solution using the solvent (e) so that the content of the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less. For example, 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 still more preferably 15 to 25% by mass.
(f) The content of the dispersant is not particularly limited, and is usually 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, of the total solid content of the photosensitive coloring composition. When the lower limit value is not less than the above-mentioned lower limit value, sufficient dispersibility tends to be easily obtained, and when the upper limit value is not more than the above-mentioned upper limit value, the ratio of other components tends to be relatively reduced, whereby the reduction in sensitivity, platemaking property, and the like tends to be suppressed. For example, the combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, even more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
The content of the dispersant (f) is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass or less, particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the colorant (a). When the lower limit value is not less than the above-mentioned lower limit value, sufficient dispersibility tends to be easily obtained, and when the upper limit value is not more than the above-mentioned upper limit value, the ratio of other components tends to be relatively reduced, and the reduction in sensitivity, platemaking property, and the like tends to be suppressed. For example, 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.
On the other hand, the content of the (b) alkali-soluble resin is usually 80 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further preferably 200 parts by mass or more, and particularly preferably 250 parts by mass or more, and is usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less, with respect to 100 parts by mass of the (d) ethylenically unsaturated compound. When the lower limit value is not less than the above-described lower limit value, there is a tendency that an appropriate dissolution development state without peeling or the like can be obtained, and when the upper limit value is not more than the above-described upper limit value, there is a tendency that an appropriate dissolution time can be obtained for the developer. The combination of the upper limit and the lower limit is, for example, preferably 80 to 700 parts by mass, more preferably 100 to 500 parts by mass, still more preferably 150 to 400 parts by mass, particularly preferably 200 to 300 parts by mass, and most preferably 250 to 300 parts by mass.
When the adhesion improver is used, the content thereof is not particularly limited, and is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass in the entire solid content of the photosensitive coloring composition. When the content ratio of the adhesion improver is equal to or higher than the lower limit, the effect of improving adhesion tends to be sufficiently obtained, and when the content ratio is equal to or lower than the upper limit, the sensitivity may be reduced, and the occurrence of defects due to residues remaining after development tends to be suppressed.
When a surfactant is used, the content thereof is not particularly limited, and is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass, of the total solid content of the photosensitive coloring composition. When the content ratio of the surfactant is equal to or higher than the lower limit value, smoothness and uniformity of the coating film tend to be easily exhibited, and when the content ratio is equal to or lower than the upper limit value, smoothness and uniformity of the coating film tend to be easily exhibited, and deterioration of other characteristics also tend to be suppressed.
< Properties of photosensitive coloring composition >
The photosensitive colored composition of the present invention can be suitably used for the formation of a colored spacer, and preferably exhibits a black color from the viewpoint of use as a colored spacer. The Optical Density (OD) corresponding to a film thickness of 1 μm of the coating film is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.3 or more, still further preferably 1.4 or more, particularly preferably 1.5 or more, and most preferably 1.8 or more, and is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less. For example, 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, further preferably 1.4 to 3.0, particularly preferably 1.5 to 3.0, and most preferably 1.8 to 2.5.
The transmittance at a wavelength of 700nm of the photosensitive coloring composition of the present invention is preferably 2.5% or less, more preferably 2.0% or less, further preferably 1.5% or less, and usually 0.01% or more. By setting the upper limit value or less, light leakage at a wavelength of 700nm can be suppressed, and a displayed image tends to be suppressed from being reddish. 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%.
On the other hand, the transmittance at a wavelength of 900nm of the photosensitive coloring composition of the present invention is preferably 10% or more, more preferably 15% or more, further preferably 20% or more, and is 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 still more preferably 20 to 100%.
In general, since the color filter including the black matrix and the pixels is directly formed on the glass substrate, alignment of the photomask for forming the black matrix does not become a problem. On the other hand, the colored spacer may be formed on the array substrate (TFT-side substrate), and in this case, the colored spacer needs to be formed in accordance with the position of the TFT pattern on the substrate. As a method of forming the colored spacer at a predetermined position, a method of performing alignment of a photomask by reading a mark on the array substrate with light having a wavelength of about 900nm may be mentioned, but in the alignment, since the mark is covered with a coating film for forming the colored spacer, it is important that the transmittance of the coating film at a wavelength of 900nm is a predetermined value or more. Therefore, when the transmittance at a wavelength of 900nm or more is set to the lower limit or more, 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 700nm and 900nm may be measured by forming a cured film having a film thickness of 2.5 μm using the photosensitive coloring composition and measuring the transmittance at a wavelength of 700nm and 900nm using a spectrophotometer. The detailed measurement conditions and the like are not particularly limited, and the measurement can be performed by the methods described in examples described later.
< method for producing photosensitive coloring composition >
The photosensitive coloring composition (hereinafter, may be referred to as "resist") of the present invention can be prepared by a usual method.
In general, the colorant (a) is preferably subjected to dispersion treatment in advance using a paint shaker, sand mill, ball mill, roll mill, stone mill, air mill, homogenizer, or the like. By the dispersion treatment, (a) the colorant is micronized, and therefore, the coating characteristics of the resist are improved.
The dispersion treatment is usually preferably performed in a system in which a part or all of (a) the colorant, (e) the solvent, (f) the dispersant, and (b) the alkali-soluble resin are used in combination (hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion liquid"). In particular, the use of a polymeric dispersant as the dispersant (f) is preferable because thickening of the resulting ink and resist with time can be suppressed (excellent dispersion stability).
Therefore, in the step of producing a resist, it is preferable to produce a colorant dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant.
As the (a) colorant, (e) organic solvent and (f) dispersant which can be used in the colorant dispersion liquid, those which can be used in the photosensitive coloring composition can be preferably used, respectively. In addition, as the content ratio of each colorant of the colorant (a) in the pigment dispersion liquid, those described as the content ratio in the photosensitive coloring composition can be preferably used.
When the liquid containing all the components blended in the colored resin composition is subjected to the dispersion treatment, the highly reactive component may be modified due to heat generation during the dispersion treatment. Therefore, the dispersion treatment is preferably performed in a system containing a polymer dispersant.
When the colorant (a) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. The temperature of the dispersion treatment is usually in the range of 0 ℃ to 100 ℃, preferably in the range of room temperature to 80 ℃, and the suitable time for the dispersion treatment is not the same depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and thus can be appropriately adjusted. The approximate criteria for dispersion are: the gloss of the ink was controlled so that the 20-degree specular gloss (JIS Z8741) of the resist became in the range of 50 to 300. When the gloss of the resist is low, the dispersion treatment is insufficient, and the number of coarse pigment (color material) particles remaining is large, and the developability, adhesion, resolution, and the like may be insufficient. Further, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is broken and a large amount of ultrafine particles are generated, and therefore, the dispersion stability tends to be impaired on the contrary.
The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the resist to prepare a uniform solution. In the resist production process, fine dust is sometimes mixed into the liquid, and therefore the obtained resist is desirably subjected to a filtration treatment with a filter or the like.
[ cured product ]
The photosensitive colored composition of the present invention can be cured to obtain a cured product. A cured product obtained by curing the photosensitive colored composition can be preferably used as a colored spacer.
[ colored spacer ]
Next, a colored spacer obtained by using the photosensitive colored composition of the present invention will be described according to a method for producing the same.
(1) Support body
The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. The transparent substrate is mainly used, and examples of the material thereof include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the substrate surface. Instead of the transparent substrate, it may be formed on the TFT array.
In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent and a urethane resin, or the like, as necessary.
The thickness of the transparent substrate is usually in the range of 0.05 to 10mm, preferably 0.1 to 7 mm. When a thin film forming process is performed on various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.
(2) Colored spacer
The photosensitive coloring composition of the present invention is used in the same applications as those of known photosensitive coloring compositions for color filters, and hereinafter, a specific example of a method for forming a black spacer using the photosensitive coloring composition of the present invention will be described with respect to a case where the composition is used as a color spacer (black spacer).
Generally, a photosensitive coloring composition is supplied in a film or pattern form by a method such as coating on a substrate on which a black photo spacer is to be provided, and a solvent is dried. Next, a pattern is formed by a method such as photolithography in which exposure and development are performed. Then, additional exposure and thermal curing are performed as necessary, thereby forming a black photo spacer on the substrate.
(3) Formation of colored spacers
[1] Method for supplying substrate
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. The supply method may be performed by a conventionally known method, for example, spin coating, wire bar (Wirebar) method, flow coating, die coating, roll coating, spray coating, or the like. In addition, the pattern may be formed by supplying by an ink jet method, a printing method, or the like. Among these, the use amount of the coating liquid can be greatly reduced by the die coating method, and the effect of fogging or the like attached when the spin coating method is used is completely eliminated, and generation of foreign matter or the like can be suppressed.
The amount of coating varies depending on the application, and for example, in the case of a black spacer, the amount is usually in the range of 0.5 to 10 μm, preferably 1 to 9 μm, and particularly preferably 1 to 7 μm in terms of dry film thickness. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire substrate. If the unevenness is large, a streak defect occurs in the liquid crystal panel.
However, when the black spacers having different heights are formed at one time by photolithography using the photosensitive colored composition of the present invention, the heights of the finally formed black spacers are different.
As the substrate, a known substrate such as a glass substrate can be used. In addition, the substrate surface is preferably planar.
[2] Drying method
The drying after the photosensitive coloring composition solution is supplied onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Further, a reduced-pressure drying method in which drying is performed in a reduced-pressure chamber without increasing the temperature may be combined.
The drying conditions are appropriately selected depending on the kind of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 40 to 130 ℃ for 15 seconds to 5 minutes, preferably 50 to 110 ℃ for 30 seconds to 3 minutes, depending on the kind of solvent component and the performance of the dryer to be used.
[3] Exposure method
The exposure is performed by a light source that superimposes a negative mask pattern on a coating film of the photosensitive coloring composition and irradiates ultraviolet rays or visible rays through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to a coating film of the photosensitive coloring composition; a method of disposing an exposure mask at a position distant from a coating film of the photosensitive coloring composition and projecting exposure light through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be employed. In this case, exposure may be performed in a deoxygenated atmosphere or after an oxygen barrier layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer, if necessary, in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen.
In a preferred embodiment of the present invention, when the black spacers having different heights are simultaneously formed by photolithography, for example, an exposure mask having a light-shielding portion (light transmittance of 0%) and an opening (intermediate transmission opening) having an average light transmittance smaller than that of the openings (full transmission openings) having the highest average light transmittance is used as the plurality of openings. In this method, a difference in residual film ratio is caused by a difference in average light transmittance between the intermediate transmission opening and the full transmission opening, that is, a difference in exposure amount.
For example, a method of forming a middle transmission opening portion by a matrix-like light-shielding pattern having fine polygonal light-shielding cells is known. Further, a method of controlling light transmittance by a film of a material such as chromium, molybdenum, tungsten, or silicon as an absorber is known.
The light source used for the exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, violet semiconductor laser, and near-infrared semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.
The optical filter may be of a type that can control the light transmittance of the exposure wavelength by a thin film, for example, and examples of the material in this case include Cr compounds (e.g., cr oxides, nitrides, oxynitrides, and fluorides), moSi, si, W, and Al.
The exposure dose is usually 1mJ/cm 2 At least, preferably 5mJ/cm 2 More preferably 10mJ/cm or more 2 Above, and typically 300mJ/cm 2 Below, preferably 200mJ/cm 2 Below, more preferably 150mJ/cm 2 The following.
In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, and more preferably 75 μm or more, and is usually 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.
[4] Developing method
After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of a basic compound or an organic solvent. In the aqueous solution, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment may be further contained.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinates; amphoteric surfactants such as alkylbetaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions of the development treatment are not particularly limited, and the development treatment can be carried out by any of the development methods such as a dip development method, a spray development method, a brush development method, and an ultrasonic development method at a development temperature of usually 10 to 50 ℃, preferably 15 to 45 ℃, particularly preferably 20 to 40 ℃.
[5] Additional exposure and thermal curing treatment
The substrate after development may be additionally exposed as necessary in the same manner as the above-described exposure method, or may be subjected to a heat curing treatment. The heat curing conditions at this time were as follows: the temperature is selected in the range of 100 to 280 ℃, preferably 150 to 250 ℃, and the time is selected in the range of 5 to 60 minutes.
The size, shape and the like of the colored spacer of the present invention can be adjusted according to the specification and the like of a color filter using the same, and the photosensitive colored composition of the present invention is useful particularly for simultaneously forming black spacers having different heights such as spacers and auxiliary spacers by photolithography, and in this case, the height of the spacers is usually about 2 to 7 μm, and the height of the auxiliary spacers is usually about 0.2 to 1.5 μm lower than the height of the spacers.
From the viewpoint of light-shielding properties, the Optical Density (OD) of the colored spacer of the present invention corresponding to 1 μm is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more, and is usually 4.0 or less, and preferably 3.0 or less. The Optical Density (OD) is a value measured by a method described later. For example, 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 further preferably 1.8 to 3.0.
[ color filters ]
The color filter may have red, green, and blue pixel coloring layers formed on a liquid crystal driving substrate (array substrate), or may have pixel coloring layers formed on a glass substrate as a transparent substrate.
[ image display apparatus ]
The image display device of the present invention includes the colored spacer of the present invention as described above.
For example, an image display device such as a liquid crystal display device including the colored spacer of the present invention can be manufactured by forming an alignment film on a liquid crystal driving substrate (array substrate) having the colored spacer of the present invention, bonding the alignment film to a counter substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell.
On the other hand, an image display device such as a liquid crystal display device including the color spacer of the present invention can also be manufactured by providing the color spacer of the present invention on the counter substrate side, forming a liquid crystal cell by bonding the color spacer to a liquid crystal driving substrate (array substrate), and injecting liquid crystal into the formed liquid crystal cell.
Further, as disclosed in, for example, japanese patent application laid-open No. 2014-215614, a liquid crystal alignment property can be improved by injecting a liquid crystal into a liquid crystal cell using a specific alignment substance and then irradiating the liquid crystal cell with ultraviolet rays.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
The constituents of the photosensitive coloring composition used in the following examples and comparative examples are as follows.
< alkali soluble resin-I >
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. Thereto were added dropwise 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of a monoacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., ltd.), and 8.47 parts by mass of 2,2' -azobis-2-methylbutyronitrile over 3 hours, followed by further stirring at 90 ℃ for 2 hours. Subsequently, the inside of the reaction vessel was replaced with air, and 43.2 parts by mass of acrylic acid were charged with 0.7 part by mass of tris (dimethylaminomethyl) phenol and 0.12 part by mass of hydroquinone, and the reaction was continued at 100 ℃ for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added thereto, and the mixture was reacted at 100 ℃ for 3.5 hours. The weight average molecular weight Mw of the alkali-soluble resin-I obtained above as measured by GPC was about 8400, and the acid value was 80mgKOH/g.
< alkali soluble resin-II >
"ZCR-1664H" manufactured by Nippon Kabushiki Kaisha (Mw =6500, acid value =60 mgKOH/g)
< pigment-I >
Irgaphor (registered trademark) Black S0100 CF (having a chemical structure represented by the following formula (i-1)) manufactured by BASF corporation belongs to the colorant (a 1).
[ chemical formula 43]
Figure BDA0002123220590000881
< pigment-II >
C.i. pigment blue 60, which belongs to colorant (a 2).
< pigment-III >
Carbon black "RAVEN1060U" manufactured by Birror corporation ("R1060" manufactured by Columbia corporation), which is a colorant (a 3).
< pigment-IV >
C.i. pigment blue 15.
< pigment-V >
C.i. pigment violet 29.
< pigment-VI >
"Paliogen (registered trademark)" Black L0086 "manufactured by BASF corporation, perylene Black, and an organic Black pigment other than the colorant (a 1).
< dispersant-I >
BYK-LPN21116 (acrylic A-B block copolymer comprising an A block having a quaternary ammonium salt group and a tertiary amino group in the side chain and a B block having no quaternary ammonium salt group and a tertiary amino group, having an amine value of 70mgKOH/g and an acid value of 1mgKOH/g or less) manufactured by BYK-Chemie corporation
The dispersant-I has an A block containing repeating units represented by the following formulas (1 a) and (2 a) and a B block containing repeating units represented by the following formula (3 a). The content of the repeating units represented by the following formulae (1 a), (2 a), and (3 a) in the total repeating units of the dispersant-I was 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.
[ chemical formula 44]
Figure BDA0002123220590000891
< dispersant-II >
DISPERBYK-167 (urethane polymer dispersant) manufactured by BYK-Chemie
< pigment derivative >
Solsperse12000 manufactured by Lubrizol "
< solvent-I >
PGMEA: propylene glycol monomethyl ether acetate
< solvent-II >
MB: 3-methoxy-1-butanol
< photopolymerization initiator-I >
An oxime ester initiator having the chemical structure described below.
[ chemical formula 45]
Figure BDA0002123220590000892
< photopolymerizable monomer >
DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kabushiki Kaisha
< additive >
KaYAMER PM-21 (phosphate containing methacryloyl group), manufactured by Nippon Kayaku Co., ltd
< surfactant >
Megafac F-559 manufactured by DIC Ltd "
< preparation of pigment Dispersion 1, 2, 4, 5 and 6 >
The pigment, the dispersant, the dispersion aid, the alkali-soluble resin, and the solvent described in table 1 were mixed in the mass ratio described in table 1. The mixed solution was subjected to a dispersion treatment for 3 hours at a temperature ranging from 25 to 45 ℃ with a paint shaker. As the beads, 0.5 mm. Phi. Zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the end of dispersion, the beads were separated from the dispersion by means of a filter to prepare pigment dispersions 1, 2, 4, 5 and 6. Since the viscosity greatly increases when the pigment-VI is dispersed under the same conditions as in the pigment dispersion liquid 2, the pigment dispersion liquid 6 needs to have a high content of the dispersant with respect to the pigment.
Figure BDA0002123220590000911
< preparation of pigment Dispersion 3 >
Pigment dispersion liquid 3 was prepared by dispersing the pigment, the dispersing agent, the dispersing aid, the alkali-soluble resin, and the solvent shown in table 1 in the same manner as in pigment dispersion liquids 1, 2, 4, 5, and 6 except that the pigment, the dispersing agent, the dispersing aid, the alkali-soluble resin, and the solvent were mixed in the mass ratios shown in table 1 and the dispersion treatment time was changed to 6 hours.
Examples 1 to 12 and comparative examples 1 to 5
Using the pigment dispersions 1 to 6 prepared above, each component was added so that the ratio of the solid content was the blending ratio of tables 2 to 5, PGMEA was further added so that the content ratio of the entire solid content was 19 mass%, and the mixture was stirred and dissolved to prepare a photosensitive colored composition, and the composition was evaluated by the following method.
< measurement of optical Density per unit film thickness (Unit OD value) and transmittance >
The optical density per unit film thickness was measured in the following order.
First, each of the obtained photosensitive coloring compositions was applied onto a glass substrate by a spin coater so that the film thickness after post-baking was 2.5 μm, dried under reduced pressure for 1 minute, and then dried at 90 ℃ for 90 seconds by a hot plate. Then, a high-pressure mercury lamp was used at 400mJ/cm 2 Illuminance of 45mW/cm 2 The entire surface was exposed to light under the exposure conditions of (1), and the substrate was heated at 230 ℃ for 20 minutes (post-baking), thereby obtaining a resist-coated substrate. The optical density (OD value) of the obtained substrate was measured by a transmission densitometer Gretag Macbeth D200-II, the film thickness was measured by a non-contact surface/layer cross-sectional shape measuring system VertScan (R) 2.0 manufactured by Trapa corporation, and the optical density (OD value) per unit film thickness was calculated from the Optical Density (OD) and the film thickness. The OD value is a numerical value indicating light-shielding ability, and a larger numerical value indicates higher light-shielding property.
Further, the transmittance at 700nm and 900nm was measured using the same substrate by a spectrophotometer UV-3100 (Shimadzu corporation). In this case, a glass substrate to which the photosensitive coloring composition was not applied was taken as a reference.
The transmittance at a wavelength of 700nm is an index of light leakage, and the smaller the value, the more preferable. There is a tendency to be preferably 2.5% or less.
The transmittance at a wavelength of 900nm is an index for reading the mark for mask alignment, and is preferably larger as the numerical value is larger. There is a tendency that it is preferably 10% or more.
The measurement results of the unit OD value and the transmittance are shown in tables 2 to 5.
< evaluation of Voltage Holding Ratio (VHR) and ion Density >
The Voltage Holding Ratio (VHR) and the ion density were evaluated by the following methods.
(preparation of liquid Crystal cell)
An electrode substrate a (made by EHC, glass ITO for evaluation) having an ITO film formed on the entire surface of one surface thereof and an electrode substrate B (20) (made by EHC, glass SZ-B111MIN (B) for evaluation) having an ITO film (2) formed in a 1cm square and connected to a 2mm wide extraction electrode formed at the center portion of one surface of the glass substrate were prepared. Fig. 1 is a schematic view showing the upper surface of the electrode substrate B (20).
Each photosensitive coloring composition was applied onto the electrode substrate A, vacuum-dried for 1 minute, and then prebaked on a hot plate at 90 ℃ for 90 seconds to obtain a coating film having a dry film thickness of 2.5. Mu.m. Then, the outer peripheral portion was shielded by 2mm, and the thickness was measured at 400mJ/cm using a high-pressure mercury lamp, respectively 2 Illuminance of 45mW/cm 2 The image exposure is performed under the exposure conditions of (1). Subsequently, the development was carried out by spraying with a water pressure of 0.15MPa at 25 ℃ using an aqueous solution of potassium hydroxide of about 0.1 mass% at 25 ℃, and then stopped with pure water and rinsed with a water-jet head. The shower developing time was adjusted to be about 1.6 times the time (break time) for dissolving and removing the unexposed photosensitive coloring composition layer, within a range of 10 to 120 seconds.
The electrode substrate a on which the coating film was formed was baked at 230 ℃ for 20 minutes to obtain an electrode substrate (resist substrate) on which a colored cured film (3) was formed. Then, the resist substrate was coated with a polyimide solution, prebaked at 70 ℃ for 2 minutes on a hot plate, and postbaked at 220 ℃ for 24 minutes. The resist substrate thus obtained was cut into a 2.5cm square substrate, thereby completing an electrode substrate a (8) for evaluation.
On the other hand, the electrode substrate B (20) was coated with a polyimide solution, prebaked at 70 ℃ for 2 minutes on a hot plate, and after-baked at 220 ℃ for 24 minutes, thereby completing the electrode substrate B (9) for evaluation.
Then, an epoxy resin-based sealant (5) containing silica beads having a diameter of 5 μm was applied to the outer periphery of the evaluation electrode substrate B (9) using a dispenser, and then the evaluation electrode substrate a (8) was attached in a state in which the applied surface thereof was pressed against the surface side (sealant side) of the evaluation electrode substrate B (9), thereby producing an empty cell. The prepared empty cell was heated in a hot air circulating furnace at 180 ℃ for 2 hours.
The thus obtained empty cell was filled with a liquid crystal (7) (Merck Japan, M) LC-6608), the peripheral portion was sealed with a UV curable sealant (6). The liquid crystal cell was annealed (heated at 105 ℃ C. For 2.5 hours in a hot air circulating furnace), and then heated at 18J/cm using a high-pressure mercury lamp 2 Illuminance of 40mW/cm 2 The liquid crystal cell (30) for measurement is completed by ultraviolet irradiation. In the obtained cell, the colored cured film was 1.7cm square and the electrode portion was 1cm square. FIG. 2 is a schematic side view of the completed liquid crystal cell (30) for measurement.
(evaluation of Voltage Holding Ratio (VHR))
The prepared liquid crystal cell for measurement was subjected to voltage application under conditions of voltage 5V, 2.0Hz, and frame time 1667msec, and voltage holding ratio was measured by "liquid crystal property evaluation device model-6254" manufactured by TOYO Corporation, and evaluated as an index of electrical reliability. The results are shown in tables 2 to 5, where higher voltage holding ratios are more preferable.
The results of measuring the voltage holding ratio under the same conditions except that the frequency was changed to 0.6Hz are shown in tables 2, 4 and 5.
(evaluation of ion Density)
The ion density can be measured, for example, by the method described in International Display Workshop (IDW)' 06 manuscript LCT 7-1. Since the voltage is applied slowly in the ion density measurement, the ion peak and the liquid crystal alignment peak can be measured while being distinguished from each other, and a difference in reliability in which a difference in voltage holding ratio is unlikely to occur may be measured. The impurity ions are sometimes referred to as causes of display defects such as afterimages and flickers (flickers) in the liquid crystal display device, and the ion density measurement is effective for the evaluation thereof.
In the measurement, the current was measured with time when a triangular wave having a frequency of 0.1Hz or. + -. 5V was applied to the liquid crystal cell for measurement by "liquid crystal physical property evaluation apparatus 6254 model" manufactured by TOYO Corporation, and a waveform of the temporal change in the current was obtained. The area of the peak (13) of the impurity ions in the waveform is measured to determine the ion density. Fig. 3 is a schematic diagram showing the applied voltage value (11), the measured current value (12), and the impurity ion peak (13) on the horizontal axis with 1 cycle time. The measurement results are shown in tables 2, 4 and 5.
Figure BDA0002123220590000951
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Figure BDA0002123220590000961
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Figure BDA0002123220590000971
[ Table 5]
Figure BDA0002123220590000981
It was confirmed that the coated substrates of the photosensitive coloring compositions of examples 1 to 4 and comparative examples 1 to 4 in table 2 have the same unit OD value, that is, have the same light-shielding properties, and among them, the coated substrates using the photosensitive coloring compositions of examples 1 to 4 have a sufficiently low transmittance at a wavelength of 700nm, excellent light-shielding properties against visible light in a long wavelength range, a sufficiently high transmittance at a wavelength of 900nm, and good mark reading suitability for mask alignment. It was also confirmed that the voltage holding ratio at 2.0Hz after the ultraviolet irradiation was high, and that the liquid crystal driving was not hindered even in the case of the panel manufacturing method in which the ultraviolet irradiation was performed after the liquid crystal cell was manufactured.
On the other hand, it was confirmed that the coated substrate using the photosensitive coloring composition of comparative example 1 had a low transmittance at a wavelength of 900nm and was not sufficiently suitable for reading marks for mask alignment.
Further, it was confirmed that the coated substrates using the photosensitive coloring compositions of comparative examples 2 and 3 had high transmittance at a wavelength of 700nm and insufficient light-shielding property for visible light in a long wavelength range, and light leakage occurred. In addition, it was confirmed that the coated substrate using the photosensitive colored composition of comparative example 2 had a low voltage holding ratio at 2.0Hz after the ultraviolet irradiation, and thus liquid crystal driving was inhibited.
On the other hand, it was confirmed that the transmittance at a wavelength of 900nm and the transmittance at a wavelength of 700nm of the coated substrate using the photosensitive coloring composition of comparative example 4 were not problematic, but the voltage holding ratio at 2.0Hz after the ultraviolet irradiation was low, thereby inhibiting the liquid crystal driving.
In the case where a black pigment is used in order to ensure the light-shielding property of the photosensitive coloring composition, the transmittance at a wavelength of 700nm can be sufficiently reduced because the black pigment has a high absorbance in the entire wavelength region of visible light, but the transmittance in this region is reduced because the absorbance in the infrared region is also high, and therefore, the transmittance at a wavelength of 900nm is reduced when the content of (a 1) the organic black pigment is low relative to 100 parts by mass of (a 3) the carbon black as in comparative example 1, that is, when the proportion of (a 3) the carbon black in the black pigment is high.
On the other hand, when (a 3) carbon black is not contained as in comparative example 2, the transmittance at a wavelength of 700nm of the resulting coated substrate is increased because (a 1) the organic black pigment has a high transmittance at a wavelength of 700 nm. Further, since carbon black having a high absorbance is not contained and the content of a pigment necessary for obtaining a predetermined OD value is increased, the voltage holding ratio at 2.0Hz after ultraviolet irradiation is deteriorated, and the electrical reliability is lowered.
In addition, when (a 2) c.i. pigment blue 60 is not contained as in comparative example 3, the transmittance at the wavelength of 700nm of the resulting coated substrate is increased because (a 1) the organic black pigment has a high transmittance at the wavelength of 700 nm. On the other hand, it is considered that the transmittance at a wavelength of 700nm can be reduced by further increasing the content of (a 3) carbon black, but the transmittance at a wavelength of 900nm is expected to be reduced as in comparative example 1. Therefore, it is considered difficult to achieve both the transmittance at a wavelength of 700nm and the transmittance at a wavelength of 900nm without containing (a 2) c.i. pigment blue 60.
Although it is effective to add a blue pigment to improve light leakage at a wavelength of 700nm, when an appropriate pigment type is selected as in comparative example 4, the voltage holding ratio at 2.0Hz after the ultraviolet irradiation is low, and the electrical reliability is lowered.
In contrast to these comparative examples, by using a combination of a specific organic black pigment, a blue pigment and carbon black as in examples 1 to 4 and setting the ratio of the specific organic black pigment to carbon black to an appropriate value, the transmittance at a wavelength of 900nm can be sufficiently high, the reading suitability of the mark at the mask alignment can be sufficient, and the transmittance at a wavelength of 700nm can be sufficiently low, and light leakage is unlikely to occur. In particular, by selecting c.i. pigment blue 60 as the blue pigment, the voltage holding ratio at 2.0Hz after the ultraviolet irradiation can be made high, and the electrical reliability can be improved. In particular, as is clear from comparison between example 2 and example 1 and comparison between example 1 and examples 3 and 4, the transmittance at a wavelength of 900nm can be further improved by increasing the content ratio of all the organic pigments to 100 parts by mass of carbon black.
On the other hand, it was confirmed that the photosensitive coloring compositions of examples 5 to 8 in table 3 have the same unit OD value of the coated substrate, that is, the same light-shielding property, and excellent transmittance at a wavelength of 900nm and electric reliability, and among them, the coated substrate using the photosensitive coloring composition of examples 7 and 8, particularly example 8, has very low transmittance at a wavelength of 700nm, and is particularly excellent in light-shielding property against visible light in a long wavelength range. From this, it is found that the transmittance at a wavelength of 700nm can be further reduced by increasing the content of (a 2) c.i. pigment blue 60 to 100 parts by mass of carbon black.
It was also confirmed that the photosensitive coloring compositions of examples 9 to 12 in table 4 had the same content ratio of all the pigments and the content ratio of the violet pigment to 100 parts by mass of the organic black pigment (a 1) was changed, and among them, the coated substrates of the photosensitive coloring compositions of examples 10 to 12, particularly examples 11 and 12 had high OD values per unit. From this, it is found that the unit OD value can be increased by increasing the content of the violet pigment relative to 100 parts by mass of the (a 1) organic black pigment.
The photosensitive coloring compositions of example 1 and comparative example 5 in table 5 have the same composition except for the kind of the organic black pigment, and it was confirmed that the photosensitive coloring composition of example 1 has a high voltage holding ratio at 2.0Hz after the ultraviolet irradiation, and thus has good electrical reliability. From this, it is found that the use of (a 1) an organic black pigment as the organic black pigment can improve the electrical reliability.
Industrial applicability
According to the photosensitive coloring composition of the invention, a cured product and a coloring spacer which have less light leakage at a wavelength of about 700nm, excellent transmittance at a wavelength of about 900nm, and excellent electrical reliability after ultraviolet irradiation can be provided, and an image display device provided with the coloring spacer can be provided. Therefore, the present invention is extremely useful industrially in various fields of photosensitive colored compositions, cured products, colored spacers, and image display devices.

Claims (11)

1. A photosensitive coloring composition, comprising: a colorant (a), an alkali-soluble resin (b), a photopolymerization initiator (c), an ethylenically unsaturated compound (d), a solvent (e), and a dispersant (f), wherein,
the (a) colorant comprises: (a1) An organic black pigment comprising at least one member 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, (a 2) C.I. pigment blue 60, and (a 3) carbon black,
the content ratio of the organic black pigment (a 1) is 150 parts by mass or more per 100 parts by mass of the carbon black (a 3),
the content ratio of the (a 2) C.I. pigment blue 60 is 150 to 400 parts by mass based on 100 parts by mass of the (a 3) carbon black,
Figure FDA0003953093730000011
in the formula (I), R 1 And R 6 Each independently is a hydrogen atom, CH 3 、CF 3 Fluorine atom or chlorine atom;
R 2 、R 3 、R 4 、R 5 、R 7 、R 8 、R 9 and R 10 Each independently is a hydrogen atom, a halogen atom, R 11 、COOH、COOR 11 、COO - 、CONH 2 、CONHR 11 、CONR 11 R 12 、CN、OH、OR 11 、COCR 11 、OOCNH 2 、OOCNHR 11 、OOCNR 11 R 12 、NO 2 、NH 2 、NHR 11 、NR 11 R 12 、NHCOR 12 、NR 11 COR 12 、N＝CH 2 、N＝CHR 11 、N＝CR 11 R 12 、SH、SR 11 、SOR 11 、SO 2 R 11 、SO 3 R 11 、SO 3 H、SO 3 - 、SO 2 NH 2 、SO 2 NHR 11 Or SO 2 NR 11 R 12 ；
And is selected from R 2 And R 3 、R 3 And R 4 、R 4 And R 5 、R 7 And R 8 、R 8 And R 9 And R 9 And R 10 Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR 11 Bridging to bond each other;
R 11 and R 12 Each independently is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
2. The photosensitive coloring composition according to claim 1, wherein the content of the organic black pigment (a 1) is 200 parts by mass or more per 100 parts by mass of the carbon black (a 3).
3. The photosensitive coloring composition according to claim 2, wherein a content ratio of the organic black pigment (a 1) is 210 parts by mass or more with respect to 100 parts by mass of the carbon black (a 3).
4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the total content of all organic pigments is 550 parts by mass or more per 100 parts by mass of the carbon black (a 3).
5. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the (a 1) organic black pigment further comprises a compound represented by the following general formula (I-2) and/or a geometric isomer of the compound,
Figure FDA0003953093730000021
6. the photosensitive coloring composition according to any one of claims 1 to 3, wherein a content ratio of the colorant (a) is 10% by mass or more in the entire solid content.
7. The photosensitive coloring composition according to any one of claims 1 to 3, wherein a content ratio of the colorant (a) is 45% by mass or less in the entire solid content.
8. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (b) contains an epoxy (meth) acrylate resin (b 1).
9. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 8.
10. A colored spacer formed from the cured product according to claim 9.
11. An image display device provided with the colored spacer according to claim 10.
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