CN114545737A - Photosensitive coloring composition for colored spacer, cured product, colored spacer, and image display device - Google Patents

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

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Publication number
CN114545737A
CN114545737A CN202210140197.3A CN202210140197A CN114545737A CN 114545737 A CN114545737 A CN 114545737A CN 202210140197 A CN202210140197 A CN 202210140197A CN 114545737 A CN114545737 A CN 114545737A
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group
pigment
acid
coloring composition
mass
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岩田训志
伊藤敦哉
小川善秀
裴丽华
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • 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
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—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

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  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides a photosensitive coloring composition for forming a coloring spacer, which has high light shielding performance, controls the height difference between a main spacer and a sub spacer, and inhibits light leakage in the whole range of wavelength of 450 nm-700 nm in a visible light region. The photosensitive coloring composition for forming a coloring spacer comprises (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent and (f) a dispersing agent, wherein the coloring agent (a) comprises (a-1) an organic pigment and (a-2) carbon black, the content of the carbon black (a-2) relative to the coloring agent (a) is 20 mass% or less, and the maximum transmittance of the photosensitive coloring composition at a wavelength of 300-370 nm is 0.010% or more.

Description

Photosensitive coloring composition for colored spacer, cured product, colored spacer, and image display device
The present application is a divisional application of the application having the application date of 2017, 2/9 and the application number of 201780010607.X, entitled "photosensitive coloring composition for a coloring spacer, cured product, coloring spacer, image display device".
Technical Field
The present invention relates to a photosensitive coloring composition for forming a colored spacer. More specifically, the present invention relates to a photosensitive coloring composition for forming a color spacer or the like, which is preferably used for forming a color spacer or the like in a filter such as a liquid crystal display, a color spacer obtained by curing the photosensitive coloring composition, and an image display device provided with the color spacer.
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 is expected to be applied to a wide range in the future because of its ease of forming a fine structure and handling a large-area substrate.
Recently, in order to cope with further higher definition and higher luminance of a Color LCD, a Color-filter-on-Array (COA) method (in which a filter is provided on a TFT (Thin Film Transistor) element substrate side, and a Black-matrix-on-Array (BOA) method (in which only a Black matrix is provided on a TFT element substrate side) have been proposed as an active matrix (active matrix) type LCD. According to this aspect, as compared with the case where the black matrix is formed on the filter side, since it is not necessary to provide a positioning device on the active element side, the aperture ratio can be increased, and as a result, the luminance can be increased. In such a black matrix structure, high light-shielding properties and suppression of light leakage in the visible light region as much as possible are required (see patent document 1).
In addition, as the panel structure and the manufacturing process become simpler, a colored spacer has been developed in which a so-called column spacer, a photo spacer, and a black matrix are integrated to keep the interval between 2 substrates in a liquid crystal panel constant. As a method for forming such a structure, a method for forming colored spacers having different heights at a time by photolithography is proposed. For example, patent document 2 discloses the following: by combining a plurality of specific pigment species having different light absorption characteristics, it is possible to realize high adhesion to the substrate while maintaining the light-shielding property and the voltage holding ratio of the liquid crystal by securing a balance between the light absorption in the ultraviolet region and the light absorption in the visible light region, and controlling the shape of the spacers and the height difference between the main spacers and the sub spacers. Patent document 3 discloses the following: by using a specific black pigment in combination with a specific dispersant, the composition is excellent in light-shielding properties, dispersibility and platemaking properties, and exhibits a sufficiently low permittivity. Patent document 4 discloses the following: by using the inorganic black colorant, the organic black colorant, and the blue colorant at a specific compounding ratio, the characteristics of the spacer and the black matrix can be satisfied at the same time.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-069822
Patent document 2: international publication No. 2013/115268
Patent document 3: international publication No. 2015/046178
Patent document 4: japanese patent laid-open publication No. 2014-146029
Disclosure of Invention
Problems to be solved by the invention
In recent years, along with the change in panel structure, it has been required for the coloring spacers to exhibit the same function as the black matrix, and particularly, it has been required to exhibit light-shielding properties without unevenness over the entire range of wavelengths from 450nm to 700nm, which is the visible light region.
The present inventors have found, as in the photosensitive coloring composition described in patent document 2, that when a coloring spacer is produced by combining a plurality of specific pigments having different light absorption characteristics, the light-shielding property is high and the difference in height between the main spacer and the sub spacer can be controlled, but the light-shielding property is not sufficient in a partial wavelength region of the visible light region, and light leakage in the entire wavelength region of 450nm to 700nm cannot be sufficiently suppressed.
Further, it was found that the photosensitive coloring composition described in patent document 3 cannot simultaneously achieve suppression of light leakage in the visible light region and control of the height difference between the main spacer and the sub spacer.
Further, it was found that the photosensitive colored composition described in patent document 4 cannot form a difference in height between the main spacer and the sub spacer.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive colored composition for forming a colored spacer, which has high light-shielding properties, can control the height difference between a main spacer and a sub spacer, and can suppress light leakage in the entire wavelength range of 450nm to 700nm, which is the visible light region.
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 an organic pigment as a colorant and carbon black in combination in a photosensitive coloring composition for forming a colored spacer, and setting the content ratio of the carbon black to a specific range and the maximum transmittance at a wavelength of 300 to 370nm to a specific range, and have completed the present invention.
That is, the present invention has the following configurations [1] to [11 ].
[1] A photosensitive coloring composition for forming a colored spacer, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, wherein,
the (a) colorant comprises (a-1) an organic pigment and (a-2) carbon black,
the content ratio of the carbon black (a-2) to the colorant (a) is 20% by mass or less, and,
the maximum transmittance of the photosensitive coloring composition at a wavelength of 300-370 nm is more than 0.010%.
[2] The photosensitive coloring composition for forming a colored spacer according to [1], wherein the organic pigment (a-1) contains at least one selected from a red pigment, an orange pigment, a blue pigment and a violet pigment.
[3] The photosensitive coloring composition for forming a colored spacer according to [1] or [2], wherein the organic pigment (a-1) contains at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.
[4] The photosensitive coloring composition for forming a colored spacer according to [1] or [2], wherein the organic pigment (a-1) contains a blue pigment and a violet pigment.
[5] The photosensitive coloring composition for forming a colored spacer according to any one of the above [1] to [4], wherein the organic pigment (a-1) contains an organic black pigment.
[6] The photosensitive coloring composition for forming a colored spacer according to [5], wherein the organic black pigment is a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound,
[ chemical formula 1]
Figure BDA0003506509350000041
(in the above formula (1), R1And R6Independently of one another, hydrogen atom, CH3、CF3Fluorine atom or chlorine atom;
R2、R3、R4、R5、R7、R8、R9and R10Independently of one another, is a hydrogen atom, a halogen atom, R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N＝CH2、N＝CHR11、N＝CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11Or SO2NR11R12；
And is selected from R2And R3、R3And R4、R4And R5、R7And R8、R8And R9And R9And R10Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR11Bridging to bond each other;
R11and R12Independently of each other, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms. )
[7] The photosensitive coloring composition for forming a colored spacer according to any one of the above [1] to [6], wherein an average optical density of a coating film after curing, which is 1 μm per 1 μm film thickness, is 1.0 or more.
[8] The photosensitive colored composition for forming colored spacers according to any one of [1] to [7], which is used for forming colored spacers having different heights at one time by a photolithography method.
[9] A cured product obtained by curing the photosensitive coloring composition for forming a colored spacer according to any one of [1] to [8 ].
[10] A colored spacer formed from the cured product according to [9 ].
[11] An image display device comprising the colored spacer according to [10 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a photosensitive colored composition for forming a colored spacer, which has high light-shielding properties, can control the height difference between a main spacer and a sub spacer, and can suppress light leakage in the entire wavelength range of 450nm to 700nm, which is the visible light region. Further, it is possible to provide a cured product and a colored spacer which are excellent in light-shielding properties, can control the difference in height between the main spacer and the sub spacer, and can suppress light leakage in the entire wavelength range of 450nm to 700nm in the visible light region, and an image display device provided with such a colored spacer.
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" also mean the same.
The meaning of the "(co) polymer" includes both homopolymer (homopolymer) and copolymer (copolymer), and the meaning of the "acid (anhydride)", "… 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 the present specification, the percentage and the part by mass are the same as the percentage and the part by weight.
[ photosensitive coloring composition for Forming colored spacer ]
The photosensitive coloring composition for forming a colored spacer of the present invention contains the following components as essential components:
(a) coloring 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 improver such as a silane coupling agent, a coatability improver, a development improver, 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.
< (a) a colorant
The colorant (a) used in the photosensitive coloring composition for forming a colored spacer of the present invention contains an organic pigment (a-1) and carbon black (a-2). In this way, the use of an organic pigment having little ultraviolet absorption makes it easy to control the shape and level difference, and the use of carbon black in addition to the organic pigment makes it possible to achieve high light-shielding properties.
The chemical structure of the organic pigment (a-1) is not particularly limited, except for azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, and bis-azo pigments
Figure BDA0003506509350000061
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. The terms "c.i. pigment red 2" and the like listed below refer to the pigment index (c.i.).
Examples of the red pigment include 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, and 48: 1. 48: 2. 48: 3. 48: 4. 49, 49: 1. 49: 2. 50: 1. 52: 1. 52: 2. 53, 53: 1. 53: 2. 53: 3. 57 and 57: 1. 57: 2. 58: 4. 60, 63: 1. 63: 2. 64, 64: 1. 68, 69, 81: 1. 81: 2. 81: 3. 81: 4. 83, 88, 90: 1. 101, 101: 1. 104, 108: 1. 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, c.i. pigment red 48: 1. 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, 272, more preferably c.i. pigment red 149, 177, 179, 194, 209, 224, 254. In view of dispersibility and light-shielding properties, c.i. pigment red 177, 254, and 272 are preferably used, and in the case where the photosensitive coloring composition is cured by ultraviolet light, a red pigment having a low ultraviolet absorption rate is preferably used as the red pigment, and from this 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, and 79. Among them, c.i. pigment orange 38, 43, 64, 71, and 72 are preferable. In addition, c.i. pigment orange 43, 64, 72 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, an orange pigment having a low ultraviolet absorption rate is preferably used as the orange pigment, and from this viewpoint, c.i. pigment orange 64, 72 is more preferably used.
Examples of the blue pigment include c.i. pigment blue 1, 1:2, 9, 14, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56:1, 60, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among them, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 are preferable, and c.i. pigment blue 15:6 is more preferable.
In view of dispersibility and light-shielding properties, c.i. pigment blue 15: 6. 16, 60 when the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorption rate as the blue pigment, and from this viewpoint, c.i. pigment blue 60 is more preferably used.
Examples of the violet pigment include c.i. pigment violet 1, 1:1, 2:2, 3:1, 3:3, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among them, c.i. pigment violet 19, 23 and 29 are preferable, and c.i. pigment violet 23 is more preferable.
In view of dispersibility and light-shielding properties, c.i. pigment violet 23 and 29 are preferably used, and in the case where the photosensitive coloring composition is cured by ultraviolet light, a violet pigment having a low ultraviolet absorption rate is preferably used as the violet pigment, and from this viewpoint, c.i. pigment violet 29 is more preferably used.
Examples of the organic coloring pigment that can be used in addition to 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 preferable.
Examples of the yellow pigment include c.i. pigment yellow 1, 1:1, 2,3,4,5,6, 9, 10, 12, 13, 14,16, 17, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 183, 188, 193, 185, 188, 190, 194, 199, 197, 189, 197, 185, 189, 194, 199, 197, 185, 189, 197, 185, 194, and 199, 200. 202, 203, 204, 205, 206, 207, 208. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150, 180 are more preferable.
Among these, it is preferable to contain at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a violet pigment from the viewpoint of adhesion. In particular, from the viewpoint of controlling the light-shielding property, shape, and level difference, at least one or more of the following pigments are preferably contained.
Red pigment: c.i. pigment red 177, 254, 272
Orange pigment: c.i. pigment orange 43, 64, 72
Blue pigment: C.I. pigment blue 15:6, 60
A violet pigment: c.i. pigment violet 23, 29
The combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, it is preferable to contain at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment, and examples thereof include: combinations of red and blue pigments, combinations of blue and orange pigments and violet pigments, and the like.
Among these, from the viewpoint of light-shielding properties in the visible light region, particularly in the long wavelength region, a blue pigment and/or a violet pigment is preferably used. In particular, since the absorption spectrum of carbon black decreases from the short wavelength to the long wavelength and the absorption of ultraviolet region increases more than that of the organic pigment, it is preferable to use a blue pigment and/or a violet pigment in combination with carbon black, and more preferable to use a blue pigment and a violet pigment in combination with carbon black, from the viewpoint of achieving both light-shielding properties and platemaking properties.
In addition, the organic pigment preferably contains an organic black pigment from the viewpoint of light-shielding properties. From the viewpoint of light-shielding properties, it is preferable to use an organic black pigment which is a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound.
[ chemical formula 2]
Figure BDA0003506509350000091
In the formula (1), R1And R6Independently of one another, hydrogen atom, CH3、CF3Fluorine atom or chlorine atom;
R2、R3、R4、R5、R7、R8、R9and R10Independently of one another, is a hydrogen atom, a halogen atom, R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N＝CH2、N＝CHR11、N＝CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11Or SO2NR11R12；
And is selected from R2And R3、R3And R4、R4And R5、R7And R8、R8And R9And R9And R10Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR11Bridging to bond each other;
R11and R12Independently of each other, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The geometric isomer of the compound represented by the general formula (1) has the following core structure (in which a substituent in the structural formula is omitted), and the trans-trans isomer may be the most stable.
[ chemical formula 3]
Figure BDA0003506509350000092
When the compound represented by the general formula (1) 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 (1) 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.
R2、R4、R5、R7、R9And R10Independently of one another, a hydrogen atom, a fluorine atom or a chlorine atom is preferred, and a hydrogen atom is more preferred.
R3And R8Independently of one another, preferably hydrogen atom or NO2、OCH3、OC2H5Bromine atom, chlorine atom, CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2Alpha-naphthyl, beta-naphthyl, SO3H or SO3 -More preferably a hydrogen atom or SO3H。
R1And R6Independently of one another, are preferably a hydrogen atom, CH3Or CF3More preferably a hydrogen atom.
Preferably selected from R1And R6、R2And R7、R3And R8、R4And R9And R5And R10At least one of the combinations of (1) is the same, more preferably R1And R6Same, R2And R7Same, R3And R8Same, R4And R9Are identical and R5And R10The same is true.
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, a2, 2-dimethylpropyl group, an n-hexyl group, a heptyl group, an n-octyl group, a1, 1,3, 3-tetramethylbutyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.
Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl and norbornylAlkenyl, bornyl, norcarane alkyl, carane alkyl,
Figure BDA0003506509350000101
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 BDA0003506509350000102
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 BDA0003506509350000103
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 and a 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1, 3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.
The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The organic black pigment represented by the above general formula (1) is preferably a compound represented by the following general formula (2).
[ chemical formula 4]
Figure BDA0003506509350000111
Specific examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100CF (manufactured by BASF corporation).
The organic black pigment is preferably dispersed in a dispersant or a solvent by the method described later. Further, if the sulfonic acid derivative of the general formula (2) is present during dispersion, the dispersibility and the storage stability may be improved.
Further, as other organic black pigments, aniline black, xeronine black, perylene black, and the like can be given.
In the present invention, the colorant (a) contains carbon black (a-2) in addition to the organic pigment (a-1). Since (a-2) carbon black has an absorption spectrum over the entire wavelength in the visible light region, it is considered that light leakage in the entire range of wavelengths 450nm to 700nm, which is the visible light region, can be suppressed by using (a-2) carbon black. 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, # 30550, #3250, #3400, #3600, #3750, #3950, #4000, #4010, # 7B, # 9B, OIL11B, OIL30B, OIL31B, and OIL31B
Manufactured by Degussa: printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color FW1, Color Black2, Color 2 FW2V, Color 18, Color 18, Color Black FW 160, Color FW 170, Color FW200 FW S
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 PEARLS480, PEARLS130, VULCA (registered trademark) 72R, ELFTEX (registered trademark) -8
Manufactured by Columbian Carbon corporation: RAVEN (registered trademark, same as hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
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 several percent of ash, and the composition of the ash is Na, Ca, K, Mg, Al, Fe, and the like, which are mixed from raw oil, fuel oil (or gas), reaction termination water, and granulation water at the time of production, and furnace materials of a reaction furnace. 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 average particle diameter is an exponential average particle diameter and is an equivalent circle diameter obtained by particle image analysis in which particles are photographed several tens of thousands times by electron microscope observation to obtain photographs of several fields of view, and the particles of about 2000 to 3000 photographs are measured by an image processing apparatus.
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 not particularly limited, and is usually a synthetic resin, and a resin having a benzene nucleus in its structure is preferable from the viewpoint of dispersibility and dispersion stability because it has a stronger function as an 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 resin coated with the carbon black is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin, and when the amount is not less than the lower limit, the carbon black can be sufficiently coated. On the other hand, when the coating amount of the resin with carbon black is not more 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 light-shielding material 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, it is estimated that the coating of the surface of carbon black with a resin also has a function of encapsulating Ca and Na in carbon black.
In addition, dyes other than the organic pigment (a-1) and the carbon black (a-2) described above can be used. Examples of the dye that can be used as the coloring material include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
Examples of azo dyes include: 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 black5, 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. mordant red 7, c.i. mordant yellow 5, c.i. mordant black 7, and the like.
Examples of the anthraquinone-based dye 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 nitro dyes include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
These pigments are preferably used by being dispersed so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the average particle diameter is based on the number of pigment particles.
In the photosensitive coloring composition, 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 carried out at 25 ℃ on a sufficiently diluted photosensitive coloring composition (usually diluted to a pigment concentration of about 0.005 to 0.2 mass%, but when there is a recommended concentration depending on the measuring instrument, the concentration is determined).
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, epoxy (meth) acrylate resins and acrylic resins are preferable. These may be used singly or in combination.
As the alkali-soluble resin (b) used in the present invention, the following alkali-soluble resin (b1) and/or alkali-soluble resin (b2) (hereinafter, sometimes referred to as "epoxy (meth) acrylate resin containing a carboxyl group") are particularly preferably used from the viewpoint of platemaking properties.
< alkali soluble resin (b1) >)
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.
< alkali soluble resin (b2) >)
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.
Here, the epoxy resin is a material including a raw material compound before forming a resin by thermosetting, and the epoxy resin 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 having 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 and phenol or cresol and further reaction with epichlorohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin, etc. can be preferably used, and epoxy resin having an aromatic ring in the main chain in this way can be suitably used.
Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resins (for example, "Epikote (registered trademark, the same applies hereinafter)" 828 "," Epikote 1001 "," Epikote 1002 "and" Epikote 1004 "manufactured by Mitsubishi chemical corporation), epoxides obtained by reacting epichlorohydrin with alcoholic hydroxyl groups of bisphenol A type epoxy resins (for example," NER-1302 "(epoxy equivalent 323, softening point 76 ℃) manufactured by Mitsubishi chemical corporation), bisphenol F type resins (for example," Epikote 807 "," EP-4001 "," EP-4002 "and" EP-4004 "manufactured by Mitsubishi chemical corporation), epoxy resins obtained by reacting alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example," NER-7406 "(epoxy equivalent 350, softening point 66 ℃), manufactured by Mitsubishi chemical corporation), Bisphenol S-type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by mitsubishi chemical corporation), phenol novolac-type epoxy resin (for example, "EPPN-201" manufactured by mitsubishi chemical corporation, "EP-152" manufactured by mitsubishi chemical corporation, "EP-154" manufactured by Dow chemical corporation), "(o-, m-, and p-) cresol novolac-type epoxy resin (for example," EOCN (registered trademark, the same applies hereinafter) -102S "," EOCN-1020 "," EOCN-104S "manufactured by mitsubishi chemical corporation), triglycidyl isocyanurate (for example," TEPIC (registered trademark) "manufactured by nippon chemical corporation), trisphenol methane-type epoxy resin (for example," EPPN (registered trademark, the same applies hereinafter) -501 "", and, "EPN-502" and "EPPN-503", alicyclic epoxy resins ("Celloxide 2021P" and "Celloxide (registered trademark, the same applies hereinafter)" EHPE "manufactured by cellosolve chemical industries), epoxy resins obtained by glycidating a phenol resin produced by the reaction of dicyclopentadiene and phenol (" EXA-7200 "manufactured by DIC corporation and" NC-7300 "manufactured by japan chemicals, epoxy resins represented by the following general formulae (B1) to (B4), and the like. Specifically, there may be mentioned "XD-1000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B2), "ESF-300" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (B4), and the like.
[ chemical formula 5]
Figure BDA0003506509350000161
In the general formula (B1), a represents an average value and represents a number of 0 to 10, and R111Represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R present in 1 molecule111May be the same or different.
[ chemical formula 6]
Figure BDA0003506509350000171
In the general formula (B2), B represents an average value and represents a number of 0 to 10, and R121Represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R present in 1 molecule121May be the same or different.
[ chemical formula 7]
Figure BDA0003506509350000172
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 8]
Figure BDA0003506509350000173
[ chemical formula 9]
Figure BDA0003506509350000174
In the above general formulae (B3-1) and (B3-2), R131～R134And R135～R137Each 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 position.
[ chemical formula 10]
Figure BDA0003506509350000181
In the general formula (B4), p and q each independently represent an integer of 0 to 4, and R141And R142Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R143And R144Each 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, epoxy resins represented by any of the general formulae (B1) to (B4) are preferably used.
Examples of the α, β -unsaturated monocarboxylic acid or α, β -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-or p-vinylbenzoic acid, monocarboxylic acids such as an α -haloalkyl group, an alkoxy group, a halogen atom, a nitro group and a cyano group-substituted compound of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylsalicylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylsalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, and the like, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhexanoic acid, 2- (meth) acryloyloxybutyltetrahydrophthalic acid, 2- (meth) acryloyloxybutylhtylphthalic acid, 2- (meth) acryloyloxybutylhutylhydrobenzoic acid, or 2- (meth) acryloyloxybutylhutylhydromaleic acid, addition of epsilon-caprolactone to (meth) acrylic acid, a monomer obtained by adding a lactone such as β -propiolactone, γ -butyrolactone or δ -valerolactone, a monomer obtained by adding an acid (acid anhydride) such as succinic acid (anhydride), phthalic acid (anhydride) or maleic acid (anhydride) to hydroxyalkyl (meth) acrylate or pentaerythritol tri (meth) acrylate, or a (meth) acrylic acid dimer.
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 singly 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 amount of the epoxy resin is preferably in the range of 0.5 to 1.2 equivalents, and more preferably in the range of 0.7 to 1.1 equivalents, based on 1 equivalent of the epoxy group in the epoxy resin. When the amount of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group to be used is small, the amount of the unsaturated group to be introduced becomes insufficient, and the subsequent reaction with the polybasic acid and/or the acid anhydride thereof becomes insufficient. In addition, it is not advantageous to leave a large amount of epoxy groups. On the other hand, when the amount is large, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted product. In either case, the curing properties tend to deteriorate.
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 such as trimethylolpropane, pentaerythritol, dipentaerythritol, or the like may be added to introduce a multi-branched structure.
The carboxyl group-containing epoxy (meth) acrylate 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 addition reaction.
As the carboxyl group-containing epoxy (meth) acrylate resin, there can be mentioned, in addition to those listed above, carboxyl group-containing epoxy (meth) acrylate resins described in Korean laid-open patent No. 10-2013-0022955.
The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth) acrylate resin in terms of polystyrene, as measured by Gel Permeation Chromatography (GPC), is usually 1,000 or more, preferably 1,500 or more, more preferably 2,000 or more, further preferably 3,000 or more, further preferably 4,000 or more, particularly preferably 5,000 or more, and is usually 10,000 or less, preferably 8,000 or less, more preferably 6,000 or less. When the weight average molecular weight is small, the solubility in the developer tends to be high, and when the weight average molecular weight is large, the solubility in the developer tends to be low.
The acid value of the carboxyl group-containing epoxy (meth) acrylate resin is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, still more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, and particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120mgKOH/g or less, and particularly preferably 100mgKOH/g or less. When the lower limit value is not less than the above-mentioned lower limit value, there is a tendency that appropriate developing solubility can be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, there is a tendency that film dissolution can be suppressed without excessive development.
The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or in combination of 2 or more kinds thereof.
In addition, a part of the above-described carboxyl group-containing epoxy (meth) acrylate resin may be used instead of another binder resin. That is, the carboxyl group-containing epoxy (meth) acrylate resin may be used in combination with other binder resins. In this case, the proportion of the carboxyl group-containing 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, and particularly preferably 80% by mass or more.
The other binder resin that can be used in combination with the carboxyl group-containing epoxy (meth) acrylate resin is not limited as long as it is selected from resins generally used in photosensitive coloring compositions. Examples thereof include binder resins described in, for example, 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), acrylic resins are preferably used from the viewpoint of compatibility with pigments, dispersants, and the like, and acrylic resins described in japanese patent application laid-open No. 2014-137466 can be preferably used.
Examples of the acrylic resin include copolymers of an ethylenically unsaturated monomer having 1 or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b 1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b 2)").
Examples of the unsaturated monomer (b1) include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, and anhydrides thereof; mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl ester ] and phthalic acid mono [2- (meth) acryloyloxyethyl ester ]; 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 (b1) may be used alone or in combination of 2 or more.
Examples of the unsaturated monomer (b2) include:
n-substituted maleimide 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 2-10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2-10) methyl ether (meth) acrylate, 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 [5.2.1.02，6]Decane-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, 3- [ (meth) acryloyloxy groupMethyl radical](meth) acrylates such as 3-ethyloxetane;
cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.02，6]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 a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (b2) may be used alone or in combination of 2 or more.
In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) within 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 (b1) and the unsaturated monomer (b2) 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 (b1) and the unsaturated monomer (b2) 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 Nos. 2003-222717, 2006-259680, 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 as described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503
Figure BDA0003506509350000221
Radical activators such as oxadiazole derivatives, halomethyl s-triazine derivatives, and N-aryl- α -amino acids such as N-phenylamino acetic acid, N-aryl- α -amino acid salts, and N-aryl- α -amino acid esters, and α -aminoalkylphenone derivatives; oxime ester derivatives described in Japanese patent laid-open Nos. 2000-80068 and 2006-36750, and the like.
Specifically, for example, as 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, dicyclopentadienyl bis (2, 4-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 Titanium, and the like.
Further, examples of the diimidazole 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, and the like.
In addition, as halomethylation
Figure BDA0003506509350000231
Oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-
Figure BDA0003506509350000232
Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-
Figure BDA0003506509350000233
Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-
Figure BDA0003506509350000234
Diazole, 2-trichloromethyl-5-furyl-1, 3,4-
Figure BDA0003506509350000235
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, examples of α -aminoalkylphenone derivatives include: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopentylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and mixtures thereof, 4- (diethylamino) chalcone, and the like.
The oxime ester compounds are effective as photopolymerization initiators in particular from the viewpoint of sensitivity and platemaking property, and the use of an alkali-soluble resin containing a phenolic hydroxyl group is disadvantageous in terms of sensitivity, and therefore, such oxime ester compounds having excellent sensitivity are particularly useful.
Examples of the oxime ester compounds include an oxime ester compound described in International publication No. 2008/075564, an oxime ester compound described in International publication No. 2009/131189, an oxime ester compound described in Japanese patent laid-open publication No. 2011-132215, an oxime ester compound described in International publication No. 2008/078678, and an oxime ester compound described in Japanese patent laid-open publication No. 2014-500852.
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: JP-A-4-221958, JP-A-4-219756, xanthene dye described in JP-A-4-219756, JP-A-3-239703, coumarin dye having a heterocyclic ring described in JP-A-5-289335, 3-oxocoumarin compound described in JP-A-3-239703, JP-A-5-289335, tolylpyrrole dye described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-05, JP-A-59-56403, JP-A-88048-15503, JP-A-60-3505, And pigments having a dialkylaminophenyl skeleton as described in Japanese patent application laid-open Nos. H2-69, 57-168088, 5-107761, 5-210240 and 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 BDA0003506509350000241
Azole, 2- (p-diethylaminophenyl) benzo
Figure BDA0003506509350000242
Azole, 2- (p-dimethylaminophenyl) benzo [4, 5]]Benzo (b) is
Figure BDA0003506509350000243
Azole, 2- (p-dimethylaminophenyl) benzo [6, 7]]Benzo (b) is
Figure BDA0003506509350000244
Oxazole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-
Figure BDA0003506509350000245
P-dialkylaminophenyl group-containing compounds such as 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) pyridine, (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 singly 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 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.
Examples of polyfunctional olefinic monomers include: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyol such as an aliphatic polyol or an aromatic polyol with an unsaturated carboxylic acid or a polycarboxylic acid, and the like.
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 polyol and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of an aromatic polyol such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and 1,2, 3-benzenetriol triacrylate.
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.
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 Kakko Kagaku Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon synthetic chemical 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 (e) a solvent, the pigment can be 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, it is preferable to select a solvent having a boiling point in the range of 100 to 300 ℃, and it is more preferable to select a solvent having a boiling point in the range of 120 to 280 ℃. 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-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 bicyclohexyl;
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 include: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco trinner, sonal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, 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 ℃ (under the condition of pressure of 1013.25hPa, the same applies hereinafter to all boiling points). 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 particularly preferable in view 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 preferable to use 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 color materials and 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.
The content ratio 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 temperature of the composition is suppressed from being lowered, and thus problems such as a tact failure in the reduced pressure drying process and a pin hole in the prebake (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.
Preferable 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, triacetin, and the like 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 polymer 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 100,000 or less, preferably 50,000 or less.
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 polymer dispersant, and particularly preferably contains an acrylic 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 DISPERBYK 160 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, a preferable chemical structure of the urethane polymer dispersant is, for example, a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule. The dispersion resin may be treated with a quaternizing agent such as benzyl chloride to convert all or a part of the tertiary amino groups into quaternary ammonium salt groups.
Examples of the polyisocyanate compound include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4,4 '-diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, etc., aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc., alicyclic diisocyanates such as isophorone diisocyanate, 4, 4' -methylenebis (cyclohexyl isocyanate), omega '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as alpha, alpha' -tetramethylxylylene diisocyanate, etc., and mixtures thereof, Triisocyanates such as lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate and triphenyltriisocyanate thiophosphate, 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 the 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 10,000 and having 1 or 2 hydroxyl groups in the same molecule include polyether diols, polyester diols, polycarbonate diols, polyolefin diols, and the like, and those obtained by alkoxylating 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.
Examples of the polyether diol include polyether diols, polyether ester diols, and mixtures of 2 or more thereof. 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, such as poly (polyoxybutylene) adipate. The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxybutylene glycol, or a compound obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.
Examples of the polyester diol include: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof with glycols (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, aliphatic diols such as 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, and 1, 9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, aromatic diols such as benzenedimethanol and bis (hydroxyethoxy) benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine) by polycondensation, for example, polyethylene adipate, polybutylene adipate, 1, 6-hexanediol adipate, and ethylene propylene glycol adipate, 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, polycaprolactone monool, and the like, Polymethyl valerolactone 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 poly (1, 6-hexanediol) carbonate and poly (3-methyl-1, 5-pentanediol) carbonate, and the polyolefin diol includes polybutadiene diol, hydrogenated polyisoprene diol, and the like.
These may be used alone or in combination of 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 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described.
Examples of the active hydrogen, i.e., the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, include hydrogen atoms in functional groups such as a hydroxyl group, an amino group and a mercapto group, and among them, hydrogen atoms of amino groups, particularly primary amino groups, are 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-dimethylethylenediamine, N-diethylethylenediamine, n, N-dipropylethylenediamine, N-dibutylethylenediamine, N-dimethyl-1, 4-butanediamine, N-diethyl-1, 4-butanediamine, N-dipropyl-1, 4-butanediamine, N-dibutyl-1, 4-butanediamine, and the like.
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
Figure BDA0003506509350000321
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 compound 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 the 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, 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 10,000 and having 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 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 in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the molecular weight is less than 1,000, dispersibility and dispersion stability are poor, and when it exceeds 200,000, solubility is lowered, dispersibility is poor, and control of the reaction becomes difficult.
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 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 its derivatives, α -methylstyrene, N-cyclohexylmaleimide, N-phenylimidomaleimide, N-tolylimido maleimide, and the like, N-substituted maleimides such as N-benzylmaleimide, macromonomers such as acrylonitrile, vinyl acetate, poly (methyl (meth) acrylate) macromonomer, polystyrene macromonomer, poly (2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer, and the like. These may be used alone or in combination of 2 or more.
The acrylic polymer dispersant is particularly preferably an a-B or B-a-B block copolymer composed of an a block having a functional group and a B block having no functional group, and in this case, the a block may contain a partial structure derived from the monomer not having a functional group but having an unsaturated group in addition to the partial structure derived from the monomer having a functional group and having an unsaturated group, and these structures may be contained in the 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 11]
(anionic living polymerization method)
Figure BDA0003506509350000351
The above synthesisIn the scheme, Ar1Is a 1-valent organic radical, Ar2Is different from Ar1M 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 12]
(free radical living polymerization method)
(nitroxyl method)
Figure BDA0003506509350000361
(ATRP method)
Figure BDA0003506509350000362
In the above synthetic scheme, Ar1Is a 1-valent organic radical, Ar2Is different from Ar1J and k are each an integer of 1 or more, RaIs a hydrogen atom or a 1-valent organic radical, RbAnd RaAnd, instead, is a hydrogen atom or a 1-valent organic group.
For the synthesis of the acrylic polymer dispersant, the methods described in Japanese patent application laid-open No. 9-62002, P.Lutz, P.Masson et al, Polym.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 hand Haoyi-Zhan, Polymer processing, 36,366(1987), Tomura-Zhan, Zebra-Guang-Zhan, Polymer literature, 46, 189(1989), M.Kuroki, T.Aida, J.Am.Chem.sic,109,4737(1987), Zhan-Zhan, Pingpio, organic Synthesis chemistry, 43,300, D.Y.1985, Solect.W.R.147r, Hercules et al, Machil-20, Machil-Hercules et al, published methods can be adopted.
The acrylic polymer dispersant usable in the present invention may be an a-B block copolymer or a B-a-B block copolymer, and the ratio of the 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 ensured.
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.
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.
0.5 to 1.5g of a dispersant sample was precisely weighed in a100 mL beaker, dissolved in 50mL of acetic acid, and subjected to a 0.1mol/L HClO solution using an automatic titrator equipped with a pH electrode4The 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 100,000. When the amount is within the above range, good dispersibility tends to be ensured.
The specific structure of the polymeric dispersant having a quaternary ammonium salt group as a functional group is not particularly limited, but from the viewpoint of dispersibility, it is preferable to have a repeating unit represented by the following formula (i) (hereinafter, may be referred to as "repeating unit (i)").
[ chemical formula 13]
Figure BDA0003506509350000381
In the above formula (i), R31～R33Each 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, R31～R332 or more of them may be bonded to each other to form a ring structure. R34Is 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～R33In the alkyl group optionally having a substituent(s), the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, and is preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, 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, or a butyl group is 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～R33In the aryl group optionally having a substituent(s), the number of carbon atoms of the aryl group is not particularly limited, and is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, 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～R33Of the aralkyl groups optionally having substituentsThe number of carbon atoms is not particularly limited, and is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. 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.
Of these, R is preferable from the viewpoint of dispersibility31～R33Each independently is alkyl or aralkyl, particularly, R is preferred31And R33Each independently being methyl or ethyl, and R32Is phenylmethylene or phenylethylene, more preferably R31And R33Is methyl and R32Is a phenylmethylene group.
When the 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 14]
Figure BDA0003506509350000391
In the above formula (ii), R35And R36Each 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, R35And R36May be bonded to each other to form a cyclic structure, R37Is a hydrogen atom or a methyl group, and Z is a linking group having a valence of 2.
R in the above formula (ii)35And R36Wherein the alkyl group optionally having a substituent(s) may be preferably used as R in the above formula (i)31～R33But are exemplary groups.
Similarly, R is represented by the above formula (ii)35And R36Wherein the aryl group optionally having a substituent(s) may be preferably used as R in the above formula (i)31～R33But are exemplary groups.R in the above formula (ii)35And R36As the aralkyl group optionally having a substituent(s) in (1), R of the above-mentioned formula (i) can be preferably employed31～R33But are exemplary groups.
Of these, R35And R36Preferably each independently an optionally substituted alkyl group, more preferably a methyl or ethyl group.
R as the above formula (i)31～R33And R of the above formula (ii)35And R36Examples of the substituent optionally having an alkyl group, an aralkyl group or an 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-R43-radical, -COOR44A group [ wherein, R43And R44A single bond, an alkylene group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms (an alkyloxyalkyl group)]Etc., are preferably-COO-R44-a radical.
In the formula (i), Y is a counter anion-Examples thereof include Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 -And the like.
The content ratio of the repeating unit represented by the formula (i) is not particularly limited, and 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, with respect 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), from the viewpoint of dispersibility.
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.
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.
In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, may be referred to as "repeating unit (iii)") in view of improving compatibility with a binder component such as a solvent and improving dispersion stability.
[ chemical formula 15]
Figure BDA0003506509350000401
In the above formula (iii), R40Is ethylene or propylene, R41Is an alkyl group optionally having a substituent, R42Is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.
R of the above formula (iii)41In the alkyl group optionally having a substituent(s), the number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, 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 cyclic structure may contain a cyclohexyl group, a cyclohexylmethyl group, or the like. Examples of the substituent optionally having include halogenAtom, alkoxy, benzoyl, hydroxy, and the like.
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 a binder component such as a solvent.
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.
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 16]
Figure BDA0003506509350000411
In the above formula (iv), R38Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent. R39Is a hydrogen atom or a methyl group.
R of the above formula (iv)38In the alkyl group optionally having a substituent(s), the number of carbon atoms of the alkyl group 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. 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. Further, the polymer may be either linear or branchedForm is shown. Further, the cyclic structure may contain a cyclohexyl group, a cyclohexylmethyl group, or the like.
R of the above formula (iv)38In the aryl group optionally having a substituent(s), the number of carbon atoms of the aryl group is not particularly limited, and is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, 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)38In the above aralkyl group having a substituent, the number of carbon atoms of the aralkyl group is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. 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 R from the viewpoint of solvent compatibility and dispersion stability38Preferably an alkyl or aralkyl group, more preferably a methyl, ethyl or phenylmethylene group.
As R38Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. Examples of the substituent optionally contained in the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, an alkoxy group, and the like. In addition, R38The 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.
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-methacryloyl morpholine.
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 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 a repeating unit (iii), and further preferably has a 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, 1a 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, the photosensitive coloring composition of the present invention may suitably contain 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, a pigment derivative, a photoacid generator, a crosslinking agent, and the like.
(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 examples of the silane coupling agent include: (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, particularly preferred are the epoxysilanes.
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 (g1), (g2) or (g 3).
[ chemical formula 17]
Figure BDA0003506509350000441
In the above general formulae (g1), (g2) and (g3), R51Represents 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 singly 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 silicon-based surfactants are effective in view of coatability.
Examples of such surfactants include: TSF4460 (manufactured by GE Toshiba Silicone 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 Dajinki Co., Ltd.), L-77 (manufactured by Nippon Youka Co., Ltd.), FC4430 (manufactured by Sumitomo 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 dispersing 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 BDA0003506509350000451
Azines, anthraquinones, indanthrones, perylenes, perinones, diketopyrrolopyrroles
Figure BDA0003506509350000452
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 a phthalocyanine sulfonic acid derivative, a quinophthalone sulfonic acid derivative, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a diketopyrrolopyrrole sulfonic acid derivative
Figure BDA0003506509350000453
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, solubility in a solvent, particularly in a solvent used for a photosensitive coloring composition, is preferableExamples of the substance having high solubility of (2) include: diphenyl iodide
Figure BDA0003506509350000456
Dimethyl phenyl iodide
Figure BDA0003506509350000454
Phenyl (p-methoxybenzyl) iodide
Figure BDA0003506509350000455
Bis (m-nitrophenyl) iodine
Figure BDA0003506509350000457
Bis (p-tert-butylphenyl) iodide
Figure BDA0003506509350000458
Bis (p-chlorophenyl) iodide
Figure BDA0003506509350000459
Bis (n-dodecyl) iodide
Figure BDA00035065093500004510
P-isobutylphenyl (p-tolyl) iodide
Figure BDA00035065093500004511
P-isopropylphenyl (p-tolyl) iodide
Figure BDA00035065093500004512
Isodiaryl iodides
Figure BDA00035065093500004513
Or triarylsulfonium chloride, bromide, borofluoride, hexafluorophosphate, hexafluoroarsenite, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, sulfonium organoboron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, or triazine compounds such as 2-methyl-4, 6-bis (trichloromethyl) triazine and 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) triazine, but the invention is 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 18]
Figure BDA0003506509350000461
In the formula (6), R61represents-NR66R67A group or an aryl group having 6 to 12 carbon atoms, R61is-NR66R67In the case of radicals, R62、R63、R64、R65、R66And R67represents-CH2OR68Radical, R61When the aryl group has 6 to 12 carbon atoms, R62、R63、R64And R65represents-CH2OR68Radical, the remainder of R62、R63、R64、R65、R66And R67Independently of one another, represent hydrogen or-CH2OR68Wherein R is68Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Typical examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group and 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 number of carbon atoms of the alkyl group and the alkoxy group is about 1 to 6. In the above, R68The 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 19]
Figure BDA0003506509350000462
In the formula (6-1), R62、R63、R64、R65、R66And R67In the case that one of them is an aryl group, R62、R63、R64And R65represents-CH2OR68Radical, the remainder of R62、R63、R64、R65、R66And R67Independently of one another, represents a hydrogen atom or-CH2OR68Where R is68Represents a hydrogen atom or an alkyl group.
Guanamine compounds corresponding to the general formula (6), that is, R in the general formula (6)61Compounds 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 triazinone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3, 5-bis (hydroxymethyl) perhydro-1, 3,5-
Figure BDA0003506509350000471
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, 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 BDA0003506509350000472
Oxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol dimercaptopropionate, butanediol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol dimercaptopropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trimethylolethyl 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), Mercapto compounds having a heterocyclic ring such as 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, aliphatic polyfunctional mercapto compounds, and the like. These mercapto compounds may be used alone or in combination of 2 or more.
< amount of component to be added to photosensitive coloring composition >
In the photosensitive coloring composition of the present invention, the content ratio of the (a) colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, and usually preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, relative to the total solid content in the photosensitive coloring composition. When the content ratio of the colorant (a) is equal to or higher than the lower limit, a sufficient Optical Density (OD) tends to be obtained, and when the content ratio is equal to or lower than the upper limit, the level difference formability tends to be easily controlled.
The content of the organic pigment (a-1) relative to the colorant (a) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, and particularly preferably 90% by mass or more, and is preferably 99% by mass or less, more preferably 97% by mass or less, further preferably 95% by mass or less, and particularly preferably 93% by mass or less. By setting the height to be equal to or greater than the lower limit value, the height difference tends to be controlled. Further, by setting the upper limit value or less, the level difference formability tends to be easily controlled.
The content of at least one pigment selected from the group consisting of the red pigment and the orange pigment with respect to the colorant (a) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the lower limit value is set to be equal to or higher than the above-described lower limit value, there is a tendency that a sufficient Optical Density (OD) can be obtained, and when the upper limit value is set to be equal to or lower than the above-described upper limit value, there is a tendency that the level difference formability is easily controlled.
The content of at least one pigment selected from the blue pigment and the violet pigment with respect to the colorant (a) is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, further preferably 80% by mass or more, and particularly preferably 85% by mass or more, and is preferably 99% by mass or less, more preferably 97% by mass or less, further preferably 95% by mass or less, particularly preferably 93% by mass or less, and most preferably 90% by mass or less. When the lower limit value is not less than the lower limit value, light shielding properties tend to be ensured, and when the upper limit value is not more than the upper limit value, the level difference formability tends to be easily controlled.
The content of the (a-2) carbon black relative to the (a) colorant is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 7% by mass or more, and particularly preferably 8% by mass or more, and is usually 20% by mass or less, preferably 18% by mass or less, more preferably 15% by mass or less, and further preferably 13% by mass or less. When the lower limit value is not less than the lower limit value, light shielding properties in the entire wavelength range of 450nm to 700nm, which is the visible light region, tend to be easily ensured, and when the upper limit value is not more than the upper limit value, the level difference formability tends to be easily controlled.
(a) When the colorant contains the organic black pigment, the content of the organic black pigment with respect to the colorant (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the lower limit value is set to be equal to or higher than the above-described lower limit value, there is a tendency that a sufficient Optical Density (OD) can be obtained, and when the upper limit value is set to be equal to or lower than the above-described upper limit value, there is a tendency that the level difference formability is easily controlled.
The content of the (b) alkali-soluble resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, relative to 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 can be suppressed from decreasing, and thus the development failure tends to be suppressed. When the upper limit value is less than or equal to the upper limit value, the penetration of the developer into the exposed portion can be suppressed from increasing, and the sharpness (sharp) and the adhesiveness of the pixel tend to be suppressed from decreasing.
The content of the photopolymerization initiator (c) 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, and particularly preferably 3% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less, relative to the total 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.
When the (c) photopolymerization initiator and the polymerization accelerator are used together, the content of the polymerization accelerator is preferably 0.05% by mass or more, and usually 10% by mass or less, and preferably 5% by mass or less with respect to the total solid content of the photosensitive coloring composition of the present invention, and the polymerization accelerator is used in an amount of usually 0.1 to 50 parts by mass, and particularly preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (c) photopolymerization initiator. When the content ratio of the polymerization accelerator is not less than the lower limit, the sensitivity to exposure light tends to be suppressed from decreasing, and when the content ratio is not more than the upper limit, the solubility of an unexposed portion in a developer is suppressed from decreasing, and thus development failure tends to be suppressed.
The amount of the sensitizing dye to be incorporated in the photosensitive coloring composition of the present invention is usually 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less of the total solid content in the photosensitive coloring composition, from the viewpoint of sensitivity.
The content of the ethylenically unsaturated compound (d) is usually 30% by mass or less, preferably 20% by mass or less, relative to the total solid content of the photosensitive coloring composition of the present invention. When the content of the ethylenically unsaturated compound (d) is not more than the upper limit, the permeability of the developing solution into the exposed portion tends to be suppressed from increasing, and a favorable image tends to be easily obtained. The lower limit of the content of the ethylenically unsaturated compound (d) is usually 5% by mass or more, preferably 10% by mass or more.
The photosensitive coloring composition of the present invention is adjusted by using the solvent (e) so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.
The content of the dispersant (f) in the solid content of the photosensitive coloring composition 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. The content of the dispersant (f) is usually 5 parts by mass or more, more preferably 10 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 content ratio of the dispersant (f) is not less than the lower limit, sufficient dispersibility tends to be easily obtained, and when the content ratio is not more than the upper limit, the decrease in sensitivity, platemaking property, and the like tends to be suppressed by relatively decreasing the ratio of other components.
When the adhesion improver is used, the content thereof is usually 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.4% by mass or more, and is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, based on the total solid content in the photosensitive coloring composition. When the content ratio of the adhesion improver is not less than the lower limit, the effect of improving adhesion tends to be sufficiently obtained, and when the content ratio is not more than the upper limit, the sensitivity reduction and the residue remaining after development tend to be suppressed to be a defect.
When the surfactant is used, the content thereof is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.03% by mass or more, and is usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less, based on the total solid content in the photosensitive coloring composition. When the content of the surfactant is not less than the lower limit, smoothness and uniformity of the coating film tend to be easily exhibited, and when the content is not more than the upper limit, smoothness and uniformity of the coating film tend to be easily exhibited, and deterioration of other properties can be suppressed.
< Properties of photosensitive coloring composition for Forming colored spacer >
The photosensitive coloring composition for forming the coloring spacer has a maximum transmittance of 0.010% or more at a wavelength of 300 to 370 nm. When a cured product such as a spacer is formed using a photosensitive coloring composition, a step of exposure using an ultraviolet lamp is generally included. The ultraviolet lamp has a light emission spectrum which is a bright line spectrum and has a plurality of light emission peaks in a wavelength range of 300-370 nm. Therefore, in order to form a spacer having a desired height difference by using the photosensitive coloring composition, it is preferable that the transmittance of the photosensitive coloring composition at a wavelength of 300 to 370nm is sufficiently high.
The photosensitive colored composition for forming a colored spacer of the present invention has a maximum transmittance at a wavelength of 300 to 370nm of usually not less than 0.010%, preferably not less than 0.020%, more preferably not less than 0.030%, further preferably not less than 0.040%, further preferably not less than 0.045%, particularly preferably not less than 0.050%, most preferably not less than 0.055%, and usually not more than 5%. When the height of the main spacers is equal to or greater than the lower limit value, the height difference between the main spacers and the sub spacers tends to be easily formed.
As described above, the photosensitive coloring composition for forming a colored spacer of the present invention has a maximum transmittance of 0.010% or more at a wavelength of 300 to 370nm, but instead of the maximum transmittance at a wavelength of 300 to 370nm, the maximum transmittance at a wavelength of 300 to 450nm may be used as an index. The maximum transmittance at a wavelength of 300 to 450nm of the photosensitive coloring composition for forming a colored spacer of the present invention is preferably 0.1% or more, more preferably 0.15% or more, further preferably 0.2% or more, even more preferably 0.25% or more, particularly preferably 0.3% or more, particularly preferably 0.4% or more, most preferably 0.5% or more, and usually 10% or less. When the height of the main spacers is equal to or greater than the lower limit value, the height difference between the main spacers and the sub spacers tends to be easily formed.
The maximum transmittance of the photosensitive coloring composition at a wavelength of 300 to 370nm and 300 to 450nm can be determined as follows: a cured film having a film thickness of 3 μm was formed using the photosensitive coloring composition, and the transmittance at wavelengths in the range of 300 to 370nm and 300 to 450nm was measured with a spectrophotometer. The detailed measurement conditions and the like are not particularly limited, and the measurement can be performed by the following method, for example.
First, a photosensitive coloring composition was applied on a glass substrate ("AN 100" manufactured by AGC corporation) using a spin coater, and then, the resultant was dried by heating on a hot plate at 90 ℃ for 90 seconds to form a coating film. The resultant coating film was irradiated with ultraviolet rays under air, and the intensity at a wavelength of 365nm was 32mW/cm2Ultraviolet ray and exposure amount of 70mJ/cm2. Next, a developer composed of an aqueous solution containing 0.05 mass% of potassium hydroxide and 0.08 mass% of a nonionic surfactant (a-60, manufactured by kao corporation) was used to perform shower development at 25 ℃ under a water pressure of 0.15MPa, and then the development was stopped with pure water and washed with a water shower. The shower development time was adjusted to 10 to 120 seconds, and was set to 1.5 times the time for dissolution removal of the unexposed coating film. The substrate with a full coating film (solid film) obtained in the above-mentioned manner was heated in an oven at 230 ℃ for 20 minutes to cure the pattern, thereby obtaining a pattern substrate with a full coating film having a film thickness of 3 μm. Next, the transmittance of the substrate was measured using a spectrophotometer UV-3150 manufactured by Shimadzu corporation at wavelengths of 300 to 370nm and 300 to 450nm, using a glass substrate not coated with the photosensitive coloring composition as a control, and the measurement pitch was set to 2 nm. Then, the maximum transmittance in the wavelength ranges of 300 to 370nm and 300 to 450nm is calculated.
The specific method for setting the maximum transmittance at a wavelength of 300 to 370nm and 300 to 450nm of the photosensitive coloring composition to be not less than the lower limit is not particularly limited, but it is preferable to use a pigment having a sufficiently high maximum transmittance at a wavelength of 300 to 370nm and 300 to 450nm as a pigment of a main light absorbing component contained in the composition, particularly (a-1) an organic pigment, and it is particularly preferable to use a pigment having a sufficiently high transmittance at 365nm, which is a maximum emission wavelength generally used in an exposure step.
Specifically, when a coating film is formed using a photosensitive coloring composition having a pigment content of 30 mass% in the total solid content and a cured film having a film thickness of 1.0 μm is formed after firing, the transmittance at a wavelength of 365nm is preferably an organic pigment of 2% or more, more preferably an organic pigment having a transmittance of 5% or more, still more preferably an organic pigment having a transmittance of 10% or more, particularly preferably an organic pigment having a transmittance of 15% or more, and usually 60% or less. By using the organic pigment having the lower limit or more, there is a case where a photosensitive colored composition having a maximum transmittance at a wavelength of 300 to 370nm and a wavelength of 300 to 450nm of the lower limit or more can be easily obtained. Table 1 shows the transmittance (%) at a wavelength of 365nm when a cured film having a film thickness of 1.0 μm (the pigment content in the entire solid content is 30% by mass) is formed by firing of a typical organic pigment.
[ Table 1]
Pigment seed Transmittance at wavelength 365nm (%)
C.i. pigment orange 64 18
C.i. pigment red 177 30
C.i. pigment red 254 39
C.i. pigment red 272 16
C.i. pigment violet 23 8
C.i. pigment violet 29 27
C.I. pigment blue 15:6 1
C.i. pigment blue 60 24
C.i. pigment yellow 139 14
Irgaphor Black S0100CF (manufactured by BASF corporation) 6
The average transmittance at 365nm of all the organic pigments contained in the organic pigment (a-1) is preferably 1% or more, more preferably 3% or more, further preferably 5% or more, further preferably 10% or more, particularly preferably 15% or more, and usually 60% or less, when a cured film having a thickness of 1.0 μm is formed after firing. By setting the height to be equal to or higher than the lower limit value, the height difference between the main spacer and the sub spacer tends to be easily formed. The average value of the transmittances can be calculated by averaging the transmittance values based on the blending ratio (mass ratio) of the organic pigments contained in the entire organic pigments.
On the other hand, the photosensitive colored composition for forming a colored spacer of the present invention can be preferably used for forming a colored spacer, and preferably exhibits a black color from the viewpoint of use as a colored spacer. The Optical Density (OD) of the coating film per 1 μm of the film thickness is preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, and particularly preferably 1.8 or more, and is usually 4.0 or less, more preferably 3.0 or less.
< method for producing photosensitive coloring composition for forming colored spacer >
The photosensitive colored composition for forming a colored spacer (hereinafter, may be referred to as "resist") of the present invention can be prepared by a conventional 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, if a polymeric dispersant is used as the dispersant (f), thickening of the obtained ink and resist with time is suppressed (excellent dispersion stability) and therefore, it is preferable.
Therefore, in the step of producing a resist, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the colorant (a), the organic solvent (e) and the dispersant (f) that can be used in the pigment dispersion liquid, those that can be used in the photosensitive coloring composition can be preferably used, respectively.
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 is controlled so that the 20-degree specular gloss (JIS Z8741) of the resist falls within the range of 50-300. 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 number 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, since fine dust is often mixed into the liquid, 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 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 surface of the substrate. In addition to 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 0.05 to 10mm, preferably 0.1 to 7 mm. When a thin film forming treatment is performed on various resins, the thickness of the film is usually 0.01 to 10 μm, preferably 0.05 to 5 μm.
(2) Colored spacer
The photosensitive coloring composition of the present invention is used for the same purpose as a known photosensitive coloring composition for a color filter. Hereinafter, a specific example of a method for forming a black photo 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 colored spacer (black photo 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 (Wire bar) 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, and the difference in height between the main spacers and the sub spacers is a height difference.
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 coating film after the photosensitive coloring composition is supplied onto the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Further, a reduced-pressure drying method of drying 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; the exposure can be performed by a method in which an exposure mask is disposed at a position away from the coating film of the photosensitive coloring composition, and exposure light is projected through the exposure mask. Alternatively, the exposure may be performed by a scanning exposure method using a laser without using a mask pattern. 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.
In order to obtain colored spacers having different heights, which are composed of the main spacers and the sub spacers, it is preferable to set the exposure amount of the sub spacers to be low relative to the exposure amount of the main spacers, and the transmittance of the intermediate transmission openings to the transmittance of the full transmission openings to be 20% or less, more preferably 15% or less, and still more preferably 10% or less, as described in japanese patent application laid-open No. 2015-127748.
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, 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/cm2Above, preferably 5mJ/cm2More preferably 10mJ/cm or more2Above, and typically 300mJ/cm2Below, preferably 200mJ/cm2Below, more preferably 150mJ/cm2The 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.
Examples of the basic compound include: 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 shower 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, etc. of the colored spacer of the present invention can be suitably adjusted according to the specification 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 between a main spacer and a sub spacer by photolithography, and in this case, the height of the main spacer is usually about 2 to 7 μm and the height of the sub spacer is usually about 0.2 to 1.5 μm lower than that of the main spacer.
The shape of the colored spacer to be formed is not particularly limited, and a form in which the main spacer and the sub spacer are formed as separate pillars is generally exemplified, and in this case, the difference between the height of the main spacer and the height of the sub spacer may be used as the height difference. On the other hand, as described in japanese patent application laid-open No. 2014-146029, a method of forming a shape in which the black matrix and the column spacers are integrated with each other may be mentioned, and in this case, the difference between the height of the black matrix and the height of the column spacers may be used as the height difference.
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 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, and particularly preferably 1.8 or more, and is usually 4.0 or less, preferably 3.0 or less. The Optical Density (OD) is a value measured by a method described later.
[ optical Filter ]
The color filter of the present invention is provided with the colored spacer of the present invention as described above, and can be produced, for example, as follows: a black matrix, red, green, and blue pixel coloring layers, and a surface coating layer were stacked on a glass substrate as a transparent substrate to form a coloring spacer, and then an alignment film was formed.
An image display device such as a liquid crystal display device provided with the colored spacer of the present invention can be manufactured by forming a liquid crystal cell by bonding the color filter having the colored spacer of the present invention and a liquid crystal driving side substrate, and injecting a liquid crystal into the formed liquid crystal cell.
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.
< organic Black pigment >
Irgaphor (registered trademark) Black S0100CF (chemical structure shown in the following formula (2))
[ chemical formula 20]
Figure BDA0003506509350000591
< 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 monomethacrylate 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 parts by mass of tris (dimethylaminomethyl) phenol and 0.12 parts 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 was about 8400 and the acid value was 80mgKOH/g as measured by GPC.
< alkali soluble resin-II >
"ZCR-1642H" (MW 6500, acid value 98mg-KOH/g) manufactured by Nippon Kagaku K.K.)
< alkali-soluble resin-III >
[ chemical formula 21]
Figure BDA0003506509350000592
50g of the epoxy compound having the above structure (epoxy equivalent 264), 16.21g of methacrylic acid, 54.8g of methoxybutyl acetate, 1.272g of triphenylphosphine, and 0.032g of p-methoxyphenol were put in a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted at 90 ℃ with stirring until the acid value became 5mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.25 part by mass of Trimethylolpropane (TMP), 2.52 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 1.61 parts by mass of tetrahydrophthalic anhydride (THPA) were charged into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ℃ while stirring, to effect a reaction.
When the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, and an alkali-soluble resin-III having an acid value of 105mgKOH/g and a weight average molecular weight (Mw) of 2480 in terms of polystyrene as measured by GPC was obtained.
< dispersant-I >
"DISPERBYK-LPN 21116" manufactured by BYK-Chemie K.K. (acrylic A-B block copolymer comprising A block having quaternary ammonium salt group and tertiary amino group in the side chain and B block having no quaternary ammonium salt group and amino group, having an amine value of 70mgKOH/g and an acid value of 1mgKOH/g or less)
The dispersant-I contains a repeating unit represented by the following formulas (1a) and (2a) in the A block and a repeating unit represented by the following formula (3a) in the B block. The content of the repeating units represented by the following formulae (1a), (2a) and (3a) in the total repeating units of the dispersant-I was 11.1 mol%, 22.2 mol% and 6.7 mol%, respectively.
[ chemical formula 22]
Figure BDA0003506509350000601
< dispersant-II >
DISPERBYK-167 (urethane polymer dispersant) manufactured by BYK-Chemie
< pigment derivative >
"Solsperse 12000" manufactured by Lubrizol corporation "
< solvent-I >
PGMEA: propylene glycol monomethyl ether acetate
< solvent-II >
MB: 3-methoxybutanol
< photopolymerization initiator-I >
[ chemical formula 23]
Figure BDA0003506509350000611
< photopolymerization initiator-II >
[ chemical formula 24]
Figure BDA0003506509350000612
< photopolymerizable monomer >
DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kabushiki Kaisha
< additive-I >
KAYAMER PM-21 (phosphate ester containing methacryloyl group), manufactured by Nippon Kabushiki Kaisha
< additive-II >
SH6040 (3-glycidoxypropyltrimethoxysilane) manufactured by DOW CORNING TORAY
< surfactant >
Megafac F-559 manufactured by DIC corporation
< evaluation of Optical Density (OD) >
The Optical Density (OD) of the glass substrate having pattern 2 described later was measured by a transmission densitometer ("D200-II" manufactured by Gretag Macbeth corporation). The film thickness at the measurement site was also measured, and the optical density (unit OD) per unit film thickness (1 μm) was calculated.
< evaluation of height Difference >
The height of the main spacer pattern corresponding to the full-transmission opening and the height of the sub spacer pattern corresponding to the intermediate-transmission opening are measured, and the difference (Δ H) between the heights is calculated. When Δ H was 0.4 μm or more, it was rated as "O", and when Δ H was less than 0.4 μm, it was rated as "X".
< transmittance in ultraviolet region >
The light transmittance of the glass substrate having pattern 2 described later was measured in the wavelength range of 300 to 450nm using a spectrophotometer UV-3150 manufactured by Shimadzu corporation, using a glass substrate not coated with the photosensitive coloring composition as a control. The measurement pitch was set to 2 nm.
The highest light transmittance in the wavelength range of 300nm to 450nm is calculated. Similarly, the maximum transmittance at a wavelength of 300nm to 370nm was calculated.
< light transmittance at wavelength 450nm to 700nm >)
The light transmittance of the glass substrate having pattern 2 described later was measured in the wavelength range of 450 to 700nm using a spectrophotometer UV-3150 manufactured by Shimadzu corporation, using a glass substrate not coated with the photosensitive coloring composition as a control. The measurement pitch was set to 2 nm.
The highest light transmittance in the wavelength range of 450 nm-700 nm is calculated.
Preparation of pigment Dispersion 1,3 to 5
The pigment, the dispersant, the dispersion aid, the alkali-soluble resin, and the solvent described in table 2 were mixed in the mass ratio described in table 2. The solution was subjected to dispersion treatment for 3 hours at 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 dispersion ends, the beads were separated from the dispersion by a filter, and pigment dispersions 1,3 to 5 were prepared.
[ Table 2]
Figure BDA0003506509350000631
< pigment Dispersion 2 (coated carbon Black Dispersion) >)
Carbon black is produced by a conventional oil furnace method. Among these, ethylene residue with a small content of Na, Ca and S was used as the feed oil, and coke oven gas was used for combustion. Further, as the reaction termination water, pure water treated with an ion exchange resin was used. 540g of the obtained carbon black was stirred with 14500g of pure water for 30 minutes at 5,000 to 6,000rpm using a homogenizer to obtain a slurry. The slurry was transferred to a vessel equipped with a screw-type stirrer, and 600g of toluene in which 60g of epoxy resin "Epikote 828" (manufactured by Mitsubishi chemical Co., Ltd.) was dissolved was added in small amounts while mixing at about 1,000 rpm. About 15 minutes, the carbon black dispersed in water was completely transferred to the toluene side, and particles of about 1mm were formed.
Subsequently, the mixture was dehydrated with a 60-mesh wire gauze, and then placed in a vacuum drier to be dried at 70 ℃ for 7 hours, thereby completely removing toluene and water.
The obtained coated carbon black, dispersant, pigment derivative and solvent were mixed in the mass ratio shown in table 2.
The mixture was sufficiently stirred by a stirrer to carry out premixing. Subsequently, dispersion treatment was performed for 6 hours at 25 to 45 ℃ by a paint shaker, and as the beads, 0.5mm phi of zirconia beads were used, and the same mass as that of the dispersion liquid was added, and after completion of the dispersion, the beads were separated from the dispersion liquid by a filter, thereby preparing a pigment dispersion liquid 2.
Examples 1 to 3 and comparative examples 1 to 4
Using the pigment dispersions 1 to 5 prepared above, the respective components were added so that the ratio of the solid content was the blending ratio in table 3, PGMEA was further added so that the solid content was 22 mass%, and they were dissolved by stirring to prepare photosensitive coloring compositions. The obtained photosensitive coloring composition was evaluated by the method described later.
[ Table 3]
Figure BDA0003506509350000641
< method for forming cured products having different heights at one time >
Each colored photosensitive composition was applied on a glass substrate ("AN 100" manufactured by AGC company) using a spin coater. Subsequently, the film was dried by heating at 90 ℃ for 90 seconds on a hot plate to form a coating film.
The obtained coating film is exposed using an exposure mask having completely transmissive openings of circular patterns of various diameters of 5 to 50 μm (5 to 20 μm: 1 μm apart, 25 to 50 μm: 5 μm apart) and intermediate transmissive openings of circular patterns of various diameters of 5 to 50 μm (5 to 20 μm: 1 μm apart, 25 to 50 μm: 5 μm apart). The intermediate transmission opening is a thin film of Cr oxide having a light transmittance of 14. + -. 2% at a wavelength of 365 nm. The exposure pitch (distance between mask and coated side) was 200. mu.m. As the irradiation light, 32 as an intensity at a wavelength of 365nm was usedmW/cm2Ultraviolet ray and exposure amount of 70mJ/cm2. In addition, ultraviolet irradiation is performed in the air.
Then, a developer prepared from an aqueous solution containing 0.05% by weight of potassium hydroxide and 0.08% by weight of a nonionic surfactant ("a-60" manufactured by kao corporation) was used, and after performing shower development at 25 ℃ under a water pressure of 0.15MPa, the development was terminated with pure water, and washing was performed with a water-washing spray. The shower developing time is adjusted to be 1.5 times the time for dissolving and removing the unexposed coating film within 10 to 120 seconds.
By the above operation, a pattern from which an unnecessary portion is removed is obtained. The substrate on which the pattern was formed was heated in an oven at 230 ℃ for 20 minutes to cure the pattern, thereby obtaining a substantially columnar spacer pattern (pattern 1). In addition, a pattern (pattern 2) of a full-coating film having a film thickness of 3 μm was formed in the same procedure except that the exposure mask was not used.
Next, the Optical Density (OD) per unit film thickness (1 μm) of the pattern 2 was measured by the method described above. The maximum light transmittance of the pattern 2 was measured in the wavelength range of 300 to 450nm, the wavelength range of 300 to 370nm, and the wavelength range of 450 to 700nm by the method described above. Further, the difference in height of the pattern 1 was evaluated by the method described above. These results are shown in table 3.
Thus, by using a photosensitive coloring composition having a maximum transmittance of 0.010% or more at a wavelength of 300 to 370nm, a level difference of a desired height can be formed in the colored spacer. In particular, by using carbon black as a colorant in addition to the organic pigment and making the content of the carbon black equal to or less than 20% by mass of the total colorant, light leakage can be suppressed without impairing the level difference.
On the other hand, a method of combining a plurality of organic pigments as in comparative example 1 was included in order to achieve a high light-shielding effect with a maximum transmittance of 0.010% or more at a wavelength of 300 to 370 nm. However, when a plurality of organic pigments having different absorption spectra are used in combination, the transmittance in a specific wavelength range is partially increased, that is, the light-shielding property in a specific wavelength range is partially insufficient, and light leakage tends to occur. For example, depending on the combination of the pigment species used, the transmittance may be partially increased in the short wavelength region or the long wavelength region.
Therefore, as in examples 1 to 5, by using carbon black having an absorption spectrum over the entire range of wavelengths in the visible light region in addition to the organic pigment, it is possible to reduce the transmittance even in the specific wavelength range described above, and in particular, by setting the content of carbon black to 20 mass% or less in the entire colorant, it is possible to suppress light leakage in the entire range of wavelengths 450nm to 700nm, which is the visible light region, without impairing the level difference formability described above.
On the other hand, a method of adding a specific blue pigment to a mixed system of an organic black pigment and carbon black as in comparative example 2 is known. However, since the maximum transmittance at a wavelength of 300 to 370nm is low, it is difficult to form a desired level difference.
Further, a method of using an organic black pigment in combination with a specific blue pigment as in comparative example 3 is also known, but since the transmittance is partially increased in a specific wavelength range as in comparative example 1 because carbon black is not contained, the suppression of light leakage in the entire range of wavelengths 450nm to 700nm, which is a visible light region, is insufficient. Further, since the pigment concentration is low, the curing component such as an alkali-soluble resin and a photopolymerizable monomer is large, and it is difficult to control the level difference.
When the content of the carbon black having high ultraviolet absorptivity exceeds 20% by mass in the entire colorant as in comparative example 4, it is considered that the maximum transmittance at a wavelength of 300 to 370nm is low, and the pattern corresponding to the intermediate transmission opening is insufficiently cured, and the pattern is peeled off during development.
The present invention has been described in detail using the specific embodiments, but it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. It is to be noted that the present application was made based on japanese patent application laid out on 12/2016 (japanese patent application 2016-.
Industrial applicability
According to the photosensitive colored composition for forming a colored spacer of the present invention, a cured product and a colored spacer which have high light-shielding properties, in which the difference in height between the main spacer and the sub spacer is controlled, and in which light leakage in the entire wavelength range of 450nm to 700nm, which is the visible light region, is suppressed, and an image display device provided with such a colored spacer can be provided. Therefore, the present invention has extremely high industrial applicability in various fields of a photosensitive colored composition for forming a colored spacer, a cured product, a colored spacer, and an image display device.

Claims (11)

1. A photosensitive coloring composition for forming a colored spacer, comprising: (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, wherein,
the (a) colorant comprises (a-1) an organic pigment and (a-2) carbon black,
the content ratio of the carbon black (a-2) to the colorant (a) is 20% by mass or less, and,
the maximum transmittance of the photosensitive coloring composition at a wavelength of 300-370 nm is more than 0.010%.
2. The photosensitive coloring composition for forming a colored spacer according to claim 1, wherein the organic pigment (a-1) contains at least one selected from a red pigment, an orange pigment, a blue pigment and a violet pigment.
3. The photosensitive coloring composition for forming a colored spacer according to claim 1 or 2, wherein the organic pigment (a-1) contains at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.
4. The photosensitive coloring composition for forming a colored spacer according to claim 1 or 2, wherein the organic pigment (a-1) contains a blue pigment and a violet pigment.
5. The photosensitive coloring composition for forming a colored spacer according to any one of claims 1 to 4, wherein the organic pigment (a-1) contains an organic black pigment.
6. The photosensitive coloring composition for forming a colored spacer according to claim 5, wherein the organic black pigment is a compound represented by the following formula (1), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound,
Figure FDA0003506509340000011
in the above formula (1), R1And R6Independently of one another, a hydrogen atom, CH3、CF3Fluorine atom or chlorine atom;
R2、R3、R4、R5、R7、R8、R9and R10Independently of one another, is a hydrogen atom, a halogen atom, R11、COOH、COOR11、COO-、CONH2、CONHR11、CONR11R12、CN、OH、OR11、COCR11、OOCNH2、OOCNHR11、OOCNR11R12、NO2、NH2、NHR11、NR11R12、NHCOR12、NR11COR12、N＝CH2、N＝CHR11、N＝CR11R12、SH、SR11、SOR11、SO2R11、SO3R11、SO3H、SO3 -、SO2NH2、SO2NHR11Or SO2NR11R12；
And is selected from R2And R3、R3And R4、R4And R5、R7And R8、R8And R9And R9And R10Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR11Bridging to bond each other;
R11and R12Independently of each other, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
7. The photosensitive coloring composition for forming a colored spacer according to any one of claims 1 to 6, wherein an average optical density per 1 μm film thickness of a coating film after curing is 1.0 or more.
8. The photosensitive coloring composition for forming colored spacers according to any one of claims 1 to 7, which is used for forming colored spacers having different heights at one time by photolithography.
9. A cured product obtained by curing the photosensitive coloring composition for forming a coloring spacer 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.
CN202210140197.3A 2016-02-12 2017-02-09 Photosensitive coloring composition for colored spacer, cured product, colored spacer, and image display device Pending CN114545737A (en)

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