CN114270263A - Photosensitive coloring composition, cured product, image display device, and pigment dispersion liquid for image display device - Google Patents

Photosensitive coloring composition, cured product, image display device, and pigment dispersion liquid for image display device Download PDF

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CN114270263A
CN114270263A CN202080057857.0A CN202080057857A CN114270263A CN 114270263 A CN114270263 A CN 114270263A CN 202080057857 A CN202080057857 A CN 202080057857A CN 114270263 A CN114270263 A CN 114270263A
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力武信夫
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Mitsubishi Chemical Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Abstract

The invention provides a photosensitive coloring composition which has excellent electrical reliability after ultraviolet irradiation and good solvent resistance. The photosensitive coloring composition of the invention comprises: (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 optical density of a coating film obtained by curing the photosensitive coloring composition per 1 [ mu ] m film thickness is 0.5 or more, and (f) a dispersantA dispersant (f1) containing a repeating unit represented by the general formula (1). (in the formula (1), Y‑Is a counter anion represented by the general formula (2). )

Description

Photosensitive coloring composition, cured product, image display device, and pigment dispersion liquid for image display device
Technical Field
The present invention relates to a photosensitive coloring composition, a cured product, an image display device, and a pigment dispersion liquid for an image display device. More particularly, the present invention relates to a photosensitive coloring composition for forming a color spacer in an image display device such as a liquid crystal display, a cured product obtained by curing the photosensitive coloring composition, and an image display device including the cured product.
The present application claims priority based on Japanese patent application No. 2019-.
Background
A Liquid Crystal Display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by the on/off action 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 easy to form a fine structure and to process a substrate for a large screen, and for the above reasons, the application range thereof tends to be further widened in the future.
However, in an LCD produced using a photosensitive composition, a voltage applied to a liquid crystal cannot be maintained due to the influence of the electrical characteristics of the photosensitive composition itself and impurities contained in the photosensitive composition, and thus, a problem of display unevenness of a display may occur. In particular, the influence is more significant in a member closer to the liquid crystal layer in a color liquid crystal display, for example, a so-called column spacer, a photo spacer, or the like used in a liquid crystal panel to keep the interval between 2 substrates constant.
Conventionally, when a spacer having no light-shielding property is used in a TFT-type LCD, a TFT as a switching element may malfunction due to light transmitted through the spacer. In order to prevent this, a method using a spacer having a light-shielding property (colored spacer) has been studied.
In recent years, along with the change in panel structure, a method of forming a colored spacer at once by photolithography has been proposed. For example, patent document 1 discloses a photosensitive coloring composition having excellent reliability, which is excellent in light-shielding properties and in which elution of impurities into a solvent is suppressed by using a combination of a plurality of organic coloring pigments and a specific photopolymerization initiator.
Patent document 2 discloses a coloring composition having excellent light-shielding properties in the visible light region and excellent transmittance in the near infrared region, which is obtained by using a specific coloring agent in combination with a dispersant having a specific structure such as an amino group.
Patent document 3 discloses that a block copolymer having a specific anion is excellent in heat resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-164623
Patent document 2: japanese patent laid-open publication No. 2018-169539
Patent document 3: international publication No. WO2018/079659
Disclosure of Invention
Problems to be solved by the invention
With the recent change in panel structure, a method of irradiating ultraviolet rays after the production of a liquid crystal cell has been widely adopted in order to improve the liquid crystal alignment properties. When ultraviolet light is irradiated, a part of the pigment contained in the colored spacer or the like tends to be decomposed to generate impurities, and sufficient electrical reliability is required to be maintained even in this case.
The present inventors have studied on a photosensitive coloring composition containing a dispersant described in patent document 1 and found that it is difficult to ensure electrical reliability after ultraviolet irradiation.
The photosensitive coloring composition containing a dispersant described in patent document 2 has insufficient chemical resistance (NMP resistance) against a solvent (N-methylpyrrolidone, NMP) when forming an alignment film.
The photosensitive coloring composition containing a dispersant described in patent document 3 is difficult to ensure electrical reliability before and after ultraviolet irradiation.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive coloring composition having excellent electrical reliability after ultraviolet irradiation and excellent solvent resistance.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that the above problems can be solved by using a specific dispersant, thereby completing the present invention.
That is, the gist of the present invention is as follows.
[1] A photosensitive coloring composition, 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,
the optical density of the coating film per 1 [ mu ] m film thickness after the photosensitive coloring composition is cured is more than 0.5,
the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1),
[ chemical formula 1]
Figure BDA0003506505710000031
(in the formula (1), R1～R3Each independently is an optionally substituted alkyl group or an optionally substituted aryl group, optionally R1～R32 or more of them are bonded to each other to form a ring structure,
R4is a hydrogen atom or a methyl group,
x is a linking group having a valence of 2,
Y-is a counter anion represented by the following general formula (2). ),
[ chemical formula 2]
Figure BDA0003506505710000032
(in the formula (2), R5Is an alkyl group optionally having a substituent. ).
[2] The photosensitive coloring composition according to the above [1], wherein the colorant (a) comprises 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.
[3] The photosensitive coloring composition according to [1] or [2], wherein the colorant (a) comprises a black pigment.
[4] The photosensitive coloring composition according to [3], wherein the black pigment comprises an organic black pigment.
[5] The photosensitive coloring composition according to any one of the above [1] to [4], wherein a content ratio of the colorant (a) is 10% by mass or more in the entire solid content.
[6] The photosensitive coloring composition according to any one of the above [1] to [5], wherein the amine value of the dispersant (f1) is 30mgKOH/g or more.
[7] The photosensitive colored composition according to any one of the above [1] to [6], which is used for forming a colored spacer.
[8] A cured product obtained by curing the photosensitive colored composition according to any one of the above [1] to [7 ].
[9] An image display device comprising the cured product according to [8 ].
[10] A pigment dispersion liquid for an image display device, comprising: (a) a colorant, (e) a solvent, and (f) a dispersant, wherein,
the (a) colorant contains a black pigment,
the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1),
[ chemical formula 3]
Figure BDA0003506505710000041
(in the formula (1), R1～R3Each independently is an optionally substituted alkyl group or an optionally substituted aryl group, optionally R1～R32 or more of them are bonded to each other to form a ring structure,
R4is a hydrogen atomOr a methyl group, or a mixture of methyl and ethyl,
x is a linking group having a valence of 2,
Y-is a counter anion represented by the following general formula (2). ),
[ chemical formula 4]
Figure BDA0003506505710000042
(in the formula (2), R5Is an alkyl group optionally having a substituent. ).
[11] The pigment dispersion liquid for an image display device according to [10], wherein the black pigment comprises an organic black pigment.
[12] The pigment dispersion liquid for an image display device according to [10] or [11], wherein the amine value of the dispersant (f1) is 30mgKOH/g or more.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a photosensitive coloring composition having excellent electrical reliability after ultraviolet irradiation and good solvent resistance.
Detailed Description
The present invention is not limited to the following embodiments, and can be carried out with various modifications within the scope of the gist thereof.
In the present invention, "(meth) acryl" means "acryl and/or methacryl", "(meth) acrylate" and "(meth) acryl" are also the same.
The term "(co) polymer" is intended to include both homopolymers (homopolymers) and copolymers (copolymers), and the terms "acid (anhydride)", "… acid (anhydride)" are intended to include both acids and their anhydrides.
In the present invention, "acrylic resin" refers to a (co) polymer containing (meth) acrylic acid, a (co) polymer containing a (meth) acrylate having a carboxyl group.
In the present invention, the term "monomer" is a term which is opposite to a so-called high molecular substance (polymer), and includes a dimer, a trimer, and an oligomer in addition to a 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 pigment dispersion liquid.
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 the base per 1g of the solid content of the dispersant. The measurement method will be described later. Unless otherwise specified, the "acid value" represents an acid value converted into an effective solid content, and is calculated by neutralization titration.
With respect to pigments, "c.i." means color index.
In the present specification, the percentage and the part represented by "mass" have the same meanings as those of the percentage and the part represented by "weight".
[ photosensitive coloring composition ]
The photosensitive coloring composition of the 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) Dispersing agent
If necessary, the composition further contains other compounding ingredients such as an adhesion improver such as a silane coupling agent, a surfactant, a pigment derivative, a photoacid generator, a crosslinking agent, a mercapto compound, and a polymerization inhibitor, and each compounding ingredient is usually used in a state of being dissolved or dispersed in a solvent.
< (a) a colorant
The photosensitive coloring composition of the present invention contains (a) a colorant. By containing the colorant (a), appropriate light absorption can be obtained, and particularly, appropriate light blocking properties can be obtained when the composition is used for forming a light blocking member such as a colored spacer.
The optical density per 1 μm of the film thickness of the coating film after curing of the photosensitive coloring composition of the present invention (hereinafter, sometimes referred to as "OD per unit film thickness") is 0.5 or more. When the colorant (a) is contained and the OD per unit film thickness is set to the lower limit value or more, the light-shielding property of the obtained cured product, particularly the colored spacer, is improved.
The OD per unit film thickness can be calculated as follows: the optical density and the film thickness of the coating film obtained by curing the photosensitive coloring composition were measured, and the optical density was divided by the film thickness. The conditions for forming the coating film are not particularly limited, and for example, the conditions described in examples described later can be employed.
In order to make the OD per unit film thickness equal to or higher than the lower limit value, for example, the kind of the colorant (a) and the content ratio of the total solid content may be appropriately adjusted.
The type of the colorant (a) that can be used in the photosensitive coloring composition of the present invention is not particularly limited, and a pigment or a dye may be used. Among these, pigments are preferably used from the viewpoint of durability.
(a) The pigment contained in the colorant may be a single pigment or 2 or more pigments. In particular, from the viewpoint of having both uniform light shielding in the visible light region and OD per unit film thickness, 2 or more are preferable.
The type of pigment that can be used as the colorant (a) is not particularly limited, and examples thereof include organic colored pigments and black pigments. The organic color pigment is an organic pigment that exhibits a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment and a yellow pigment.
Among the pigments, organic colored pigments are preferably used from the viewpoint of suppressing absorption of ultraviolet rays and easily controlling the shape and height difference of the cured product. In addition, from the viewpoint of light-shielding properties, a black pigment is preferably used.
The organic coloring pigment may be used alone or in combination of 2 or more. In particular, from the viewpoint of making the OD per unit film thickness 0.5 or more, it is more preferable to use a combination of organic color pigments having different colors, and it is further preferable to use a combination of organic color pigments that exhibit a color close to black.
The chemical structure of these organic coloring pigments is not particularly limited, and examples thereof include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, bisindolinone
Figure BDA0003506505710000071
Oxazines, indanthrene, perylene, and the like. Specific examples of pigments that can be used are shown below by the pigment numbers. The "c.i." in "c.i. pigment red 2" and the like listed below refers to a pigment index.
As the red pigment, there can be mentioned: 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, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:2, 53:1, 53:2, 53:3, 57:1, 57:2, 58:4, 60, 63:1, 63:2, 64:1, 68, 69, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101:1, 104, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 169, 151, 166, 168, 149, 170, 172, 176, 187, 188, 207, 188, 194, 185, 194, 187, 185, 194, 187, 194, 185, 194, 187, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 200, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 194, 187, 207, 194, 187, 207, 194, 185, 194, 187, 194, 200, 194, 200, 194, 187, 194, 200, 194, 200, 194, 200, 194, 200, 194, 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, from the viewpoint of light-shielding properties and dispersibility, c.i. pigment red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, and 254 are preferable, and c.i. pigment red 177, 209, 224, and 254 are more preferable. 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, it is preferable to use a red pigment having a low ultraviolet absorption rate, and from this viewpoint, c.i. pigment red 254 and 272 are more preferably used.
As an orange (orange) pigment, c.i. pigment orange 1,2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among them, c.i. pigment orange 13, 43, 64, and 72 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use an orange pigment having a low ultraviolet light absorption rate, and from this viewpoint, c.i. pigment orange 64 and 72 are more preferably used.
As the blue pigment, there can be mentioned: 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, 79. Among them, from the viewpoint of light-shielding properties, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferable, and c.i. pigment blue 15:6 is more preferable.
In addition, c.i. pigment blue 15:6, 16, and 60 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorption rate, and from this viewpoint, c.i. pigment blue 60 is more preferably used.
As the violet pigment, there can be mentioned: 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, 50. Among them, from the viewpoint of light-shielding properties, c.i. pigment violet 19, 23, and 29 are preferable, and c.i. pigment violet 23 is more preferable.
In addition, c.i. pigment violet 23, 29 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive coloring composition is cured by ultraviolet light, it is preferable to use a violet pigment having a low ultraviolet light absorption rate, and from this viewpoint, c.i. pigment violet 29 is more preferably used.
As the green pigment, there can be mentioned: c.i. pigment green 1,2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. Among them, c.i. pigment green 7 and 36 are preferably used.
As the yellow pigment, there can be mentioned: 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, 182, 183, 188, 193, 198, 195, 185, 188, 193, 194, 198, 197, 200, 204, 197, 200, 194, 204, 199, 204, 197, 200, 204, 199, 204, 197, 204, 200, 199, 204, 200, and 204, 200, 150, 204, 150, 109, 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, at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a violet pigment is preferably used from the viewpoint of controlling the light-shielding property, shape and level difference of the cured product.
Among these, from the viewpoint of controlling the light-shielding property, shape, and level difference of the cured product, 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 of the formula
A violet pigment: c.i. pigment violet 23, 29
When 2 or more organic color pigments are used in combination, the combination of the organic color pigments is not particularly limited, and 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 from the viewpoint of light-shielding properties.
The combination of colors is not particularly limited, and from the viewpoint of light-shielding properties, for example, the following are listed: a combination of red and blue pigments, a combination of blue and orange pigments and a violet pigment.
As the black pigment, organic black pigments and inorganic black pigments can be cited. Among them, organic black pigments are preferably used from the viewpoint of suppressing absorption of ultraviolet rays and easily controlling the shape and height difference of the cured product.
Among the organic black pigments, from the viewpoint of suppressing a decrease in the voltage holding ratio of the liquid crystal and suppressing absorption of ultraviolet light to easily control the shape and the level difference, it is preferable to use an organic black pigment (hereinafter, sometimes referred to as "organic black pigment represented by" general formula (1) ") using at least one of a compound represented by the following general formula (1) (hereinafter, sometimes referred to as" compound (1) "), a geometric isomer of compound (1), a salt of compound (1), and a salt of geometric isomer of compound (1).
[ chemical formula 5]
Figure BDA0003506505710000091
In the formula (1), R11And R16Each independently represents a hydrogen atom, CH3、CF3Fluorine atom or chlorine atom;
R12、R13、R14、R15、R17、R18、R19and R20Each independently represents a hydrogen atom, a halogen atom, R21、COOH、COOR21、COO-、CONH2、CONHR21、CONR21R22、CN、OH、OR21、COCR21、OOCNH2、OOCNHR21、OOCNR21R22、NO2、NH2、NHR21、NR21R22、NHCOR22、NR21COR22、N＝CH2、N＝CHR21、N＝CR21R22、SH、SR21、SOR21、SO2R21、SO3R21、SO3H、SO3 -、SO2NH2、SO2NHR21Or SO2NR21R22；
Is selected from R12And R13、R13And R14、R14And R15、R17And R18、R18And R19And R19And R20Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR21Bridging to bond each other;
R21and R22Each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.
The compound (1) and the geometric isomer of the compound (1) have 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 6]
Figure BDA0003506505710000101
When the compound (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, alkaline earth metal, transition metal, primary amine, secondary amine or trialkylamine, or a quaternary ammonium or organometallic complex compound such as tetraalkylammonium. When the geometric isomer of the compound (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.
R12、R14、R15、R17、R19And R20Each independently is preferably a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.
R13And R18Each independently preferably represents a 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 is particularly preferably a hydrogen atom.
R11And R16Each independently preferably represents a hydrogen atom or CH3Or CF3More preferably a hydrogen atom.
Preferably selected from R11And R16、R12And R17、R13And R18、R14And R19And R15And R20At least one of the combinations of (1) is the same, more preferably R11And R16Same, R12And R17Same, R13And R18Same, R14And R19Are identical and R15And R20The 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, an n-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, norbornenyl, norcarane, carane alkyl, methyl ethyl, ethyl propyl, butyl,
Figure BDA0003506505710000111
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 BDA0003506505710000112
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 BDA0003506505710000113
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 general formula (1) is preferably an organic black pigment containing at least one selected from the group consisting of a compound represented by the following general formula (2) (hereinafter, also referred to as "compound (2)") and a geometric isomer of the compound (2).
[ chemical formula 7]
Figure BDA0003506505710000121
Examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably used after being dispersed by a dispersant, a solvent or a method described later. Further, if the sulfonic acid derivative of the compound (1), particularly the sulfonic acid derivative of the compound (2), is present during dispersion, the dispersibility and the storage stability may be improved, and therefore, it is preferable that the organic black pigment contains these sulfonic acid derivatives.
Examples of the organic black pigment other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.
On the other hand, from the viewpoint of light-shielding properties, an inorganic black pigment is preferably used.
Examples of the inorganic black pigment include: carbon black, acetylene black, lamp black, bone black, graphite, iron black, Xeronine black, titanium black. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. 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, OIL9B, OIL11B, OIL30B, OIL31B, and # 263033
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 FW2, Color FW2V, Color 18, Color Black 18, Color Black 160, Color FW 170, Color FW S200, Color FW S170, Color FW
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, the same below) XC72R, ELFTEX (registered trademark) -8
Manufactured by Birla corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
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 laid-open No. H09-71733 can be preferably used. In view of volume resistance and dielectric constant, resin-coated carbon black is preferably used.
As the carbon black to be subjected to the coating treatment with the resin, the total content of Na and Ca is preferably 100ppm or less. Carbon black generally contains ash in the order of percentage, the composition of which is Na, Ca, K, Mg, Al, Fe, and the like mixed from raw oil at the time of production, fuel oil (or gas), reaction end water, granulation water, furnace materials of a reaction furnace, and the like. Among them, Na and Ca are usually contained in an amount of several hundred ppm or more, and by reducing these amounts, penetration into the transparent electrode (ITO) and other electrodes can be suppressed, and electrical short-circuiting tends to be prevented.
As a method for reducing the content of these ashes containing Na and Ca, a method of strictly selecting substances having extremely small contents as a feedstock oil, a fuel oil (or gas), and a reaction terminating water in the production of carbon black, and a method of extremely reducing the amount of an alkali substance to be added for structure adjustment 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 about 2000 to 3000 particles of these 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 of the above example, adding carbon black, mixing, drying, removing the solvent to obtain carbon black to which carboxylic acid is attached (added), and adding resin to the carbon black 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 ring 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 carbon black to be coated 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 tends to be sufficiently coated. On the other hand, when the amount is equal to or less than the upper limit, the adhesion between the resins tends to be prevented and the dispersibility tends to be good.
The carbon black coated with the resin in this way can be used as a 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.
These pigments are preferably used after being dispersed so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the average particle diameter is based on the number of pigment particles.
In the photosensitive coloring composition of the present invention, 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 usually performed on a sufficiently diluted photosensitive coloring composition (which is usually diluted so that the pigment concentration is about 0.005 to 0.2 mass%, but is determined according to the recommended concentration of the pigment if the concentration is determined by a measuring instrument) and the measurement is performed at 25 ℃.
In the photosensitive coloring composition of the present invention, one kind of coloring agent such as an organic coloring pigment and a black pigment may be used alone, or 2 or more kinds may be used in combination. Among these, from the viewpoint of easy control of the shape and the height difference, it is preferable to use an organic black pigment and an organic coloring pigment in combination, and from the viewpoint of light-shielding property, it is preferable to use carbon black and an organic coloring pigment in combination.
In addition, dyes other than the organic coloring pigments and black pigments described above may be used. Examples of dyes that can be used as a coloring material include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
As azo dyes, there may be mentioned, for example: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active 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. medium red 7, c.i. medium yellow 5, c.i. medium black 7.
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.
Examples of the phthalocyanine dyes include c.i. vat blue 5, quinoneimine dyes include c.i. basic blue 3 and c.i. basic blue 9, quinoline dyes include c.i. solvent yellow 33, c.i. acid yellow 3 and c.i. disperse yellow 64, and examples of the nitro dyes include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
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: among epoxy (meth) acrylate resins, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolak resins, and polyvinyl phenol resins, from the viewpoint of excellent platemaking properties, it is preferable to use:
(b1) epoxy (meth) acrylate resin
(b2) An acrylic resin, a resin containing a vinyl group,
these may be used singly or in combination.
< (b1) epoxy (meth) acrylate resin
(b1) The epoxy (meth) acrylate resin is obtained by reacting a hydroxyl group generated by the reaction of an epoxy compound (epoxy resin) with an α, β -unsaturated monocarboxylic acid and/or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety with a compound having 2 or more substituents reactive with the hydroxyl group, such as a polybasic acid and/or an acid anhydride thereof.
Further, the (b1) epoxy (meth) acrylate resin is also included in the (b1) epoxy (meth) acrylate resin, which is obtained by reacting a compound having 2 or more substituents capable of reacting with a hydroxyl group before reacting the polybasic acid and/or its anhydride with the hydroxyl group, and then reacting the compound with the polybasic acid and/or its anhydride.
Further, a resin obtained by further reacting a compound having a reactive functional group with a carboxyl group of the resin obtained by the above reaction is also included in the above (b1) epoxy (meth) acrylate resin.
Therefore, epoxy (meth) acrylate resins are not limited to "(meth) acrylate" because they have substantially no epoxy group in their chemical structure, but they are conventionally named because epoxy compounds (epoxy resins) are used as raw materials and "(meth) acrylate" is a typical example thereof.
As the (b1) epoxy (meth) acrylate resin used in the present invention, the following epoxy (meth) acrylate resin (b1-1) and/or epoxy (meth) acrylate resin (b1-2) (hereinafter, may be referred to as "carboxyl group-containing epoxy (meth) acrylate resin") is particularly preferably used from the viewpoint of developability and reliability.
< epoxy (meth) acrylate resin (b1-1) >
An alkali-soluble resin obtained by adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting the resulting product with a polybasic acid and/or an acid anhydride thereof.
< epoxy (meth) acrylate resin (b1-2) >
An alkali-soluble resin obtained by adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting 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 an epihalohydrin can be used. The phenolic compound is preferably a compound having a phenolic hydroxyl group at a valence of 2 or more, and may be a monomer or a polymer.
As the kind of the raw material epoxy resin, for example, 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 a polyaddition reactant of dicyclopentadiene and phenol or cresol and further epihalohydrin, adamantyl group-containing epoxy resin, fluorene type epoxy resin can be preferably used, and among these, epoxy resin having an aromatic ring in the main chain can be more preferably used.
Further, as the epoxy resin, for example, bisphenol A type epoxy resins (for example, "JeR (registered trademark, the same shall apply hereinafter)" 828 "," JeR-1001 "," JeR-1002 "," JeR-1004 "manufactured by Mitsubishi chemical corporation), epoxy resins obtained by the reaction of the alcoholic hydroxyl group of bisphenol A type epoxy resins and epichlorohydrin (for example," NER-1302 "(epoxy equivalent 323, softening point 76 ℃ manufactured by Mitsubishi chemical corporation), bisphenol F type resins (for example," JeR-807 "," EP-4001 "," EP-4002 "," EP-4004 "manufactured by Mitsubishi chemical corporation), epoxy resins obtained by the reaction of the alcoholic hydroxyl group of bisphenol F type epoxy resins and epichlorohydrin (for example," NER-7406 "(epoxy equivalent 350, epoxy equivalent 350 manufactured by Mitsubishi chemical corporation), Softening point 66 ℃), 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", "EP-154" manufactured by mitsubishi chemical corporation, "DEN-438" manufactured by Dow chemical corporation), ("o-, m-, and p-) cresol novolac type epoxy resin (for example," EOCN (registered trademark, the same as below) "102S", "EOCN-1020", "EOCN-104S" manufactured by mitsui chemical corporation), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by nippo chemical corporation), triphenol methane type epoxy resin (for example, "EPPN (registered trademark, hereinafter, the same as above) -501 "," EPPN-502 "," EPPN-503 "), alicyclic epoxy resins (" Celloxide (registered trademark, hereinafter the same as above) "2021P" and "Celloxide EHPE" manufactured by Dailuo corporation, 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 Nippon Kagaku corporation), and epoxy resins represented by the following general formulae (B1) to (B4). Specifically, examples thereof include "XD-1000" manufactured by Nippon chemical Co., Ltd as an epoxy resin represented by the following general formula (B1, "NC-3000" manufactured by Nippon chemical Co., Ltd as an epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka organic chemical industry Co., Ltd as an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nissan iron Japan chemical Co., Ltd as an epoxy resin represented by the following general formula (B4).
[ chemical formula 8]
Figure BDA0003506505710000181
In the general formula (B1), a represents an average value and is a number of 0 to 10, and R111Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In addition, a plurality of R's present in 1 molecule111Each may be the same or different.
[ chemical formula 9]
Figure BDA0003506505710000182
In the general formula (B2), B1 and B2 are each independently an average value and represent a number of 0 to 10, R121Each independently representA 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's present in 1 molecule121Each may be the same or different.
[ chemical formula 10]
Figure BDA0003506505710000191
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 2 or 3.
[ chemical formula 11]
Figure BDA0003506505710000192
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 arm.
[ chemical formula 12]
Figure BDA0003506505710000193
In the general formula (B4), p and q each independently represent an integer of 0 to 4, 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 represents an integer of 0 or more.
Among these, epoxy resins represented by any of 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: monocarboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-or p-vinylbenzoic acid, and a halogenated alkyl group, alkoxy group, halogen atom, nitro group or cyano group-substituted compounds at the α -position of (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethyladipic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylsmaleic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, maleic acid, acrylic acid, and acrylic acid, acrylic, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acryloyloxybutylhexanoic acid, 2- (meth) acryloyloxybutylhtrahydrophthalic acid, 2- (meth) acryloyloxybutylhutylphthalic acid, 2- (meth) acryloyloxybutylhutylhymaleic acid, monomers obtained by adding a lactone such as e-caprolactone, β -propiolactone, γ -butyrolactone or δ -valerolactone to (meth) acrylic acid, monomers obtained by adding an acid (anhydride) such as succinic acid (anhydride), phthalic acid (anhydride) or maleic acid (anhydride) to hydroxyalkyl (meth) acrylate or pentaerythritol tri (meth) acrylate, and (meth) acrylic acid dimers.
Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α, β -unsaturated monocarboxylic acid or an α, β -unsaturated monocarboxylic acid ester having a carboxyl group may be reacted with an epoxy resin in the presence of an esterification catalyst at a temperature of 50 to 150 ℃. Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride.
The epoxy resin, the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of 2 or more.
The α, β -unsaturated monocarboxylic acid or α, β -unsaturated monocarboxylic acid ester having a carboxyl group is used in the following amounts: the 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 not less than the lower limit, the amount of the unsaturated group to be introduced may be suppressed from being insufficient, and the subsequent reaction with the polybasic acid and/or the anhydride thereof tends to be sufficient. On the other hand, when the amount is equal to or less than the upper limit, the amount of the unreacted product of the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed from remaining, and the curing properties tend to be improved.
Examples of the polybasic acid and/or the anhydride thereof include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthalate, endomethylene tetrahydrophthalic acid, hexachloronorbornene diacid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid, and 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, and the reaction can be continued 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 lower limit value is not less than the above-mentioned lower limit value, the alkali developability tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the curing performance tends to be good.
In addition reaction of the polybasic acid and/or the acid anhydride thereof, a polyfunctional alcohol (polyhydric alcohol) such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2, 3-propanetriol, or the like may be added to introduce a multi-branched structure. In this case, the mixing order of the polybasic acid and/or anhydride thereof and the polyfunctional alcohol is not particularly limited. Upon warming, the polybasic acid and/or its anhydride undergoes an addition reaction with respect to any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the α, β -unsaturated monocarboxylic acid or the α, β -unsaturated monocarboxylic acid ester having a carboxyl group, and the polyfunctional alcohol.
By using a polyol, the molecular weight of the (b1) epoxy (meth) acrylate resin can be increased, and a branch can be introduced into the molecule, so that there is a tendency that a balance between the molecular weight and the viscosity can be obtained. Further, the introduction rate of an acid group into a molecule can be increased, and a balance between sensitivity, adhesion, and the like tends to be easily obtained.
As the carboxyl group-containing epoxy (meth) acrylate resin, there can be mentioned, for example, those described in Korean laid-open patent publication No. 10-2013-0022955, in addition to the above-mentioned ones.
The carboxyl group-containing epoxy (meth) acrylate resin has a weight average molecular weight (Mw) of usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and usually 10000 or less, preferably 8000 or less, more preferably 7000 or less in terms of polystyrene as measured by Gel Permeation Chromatography (GPC). For example, the concentration is preferably 1000 to 10000, more preferably 1500 to 10000, further preferably 1500 to 8000, further preferably 2000 to 8000, and particularly preferably 2000 to 7000. When the lower limit value is set to be equal to or higher than the lower limit value, the solubility in the developer tends to be suppressed from becoming too high, and when the upper limit value is set to be equal to or lower than the upper limit value, the solubility in the developer tends to be improved.
The acid value of the carboxyl group-containing epoxy (meth) acrylate resin is not particularly limited, and is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, and further preferably 50mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less, and particularly preferably 100mgKOH/g or less. For example, it is preferably from 10mgKOH/g to 200mgKOH/g, more preferably from 20mgKOH/g to 150mgKOH/g, still more preferably from 40mgKOH/g to 120mgKOH/g, and yet more preferably from 50mgKOH/g to 100 mgKOH/g. When the lower limit value is not less than the lower limit value, appropriate developing solubility tends to be obtained, and when the upper limit value is not more than the upper limit value, film dissolution tends to be suppressed without excessive development.
The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, and from the viewpoint of developability and reliability, an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (b1-I) (hereinafter, may be abbreviated as "(b 1-I) epoxy (meth) acrylate resin") and/or an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (b1-II) (hereinafter, may be abbreviated as "(b 1-II) epoxy (meth) acrylate resin") is preferable.
[ chemical formula 13]
Figure BDA0003506505710000221
In the formula (b1-I), R11Represents a hydrogen atom or a methyl group, R12Represents an optionally substituted 2-valent hydrocarbon group, k represents 1 or 2, and represents a bonding arm. The benzene ring in the formula (b1-I) may be further substituted with an arbitrary substituent.
[ chemical formula 14]
Figure BDA0003506505710000222
In the formula (b1-II), R13Each independently represents a hydrogen atom or a methyl group, R14Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R15And R16Each independently represents a 2-valent aliphatic group optionally having a substituent, m and n each independently represent an integer of 0 to 2, and x represents a bonding arm.
< (b1-I) epoxy (meth) acrylate resin
First, the epoxy (meth) acrylate resin having a partial structure represented by the general formula (b1-I) will be described in detail.
[ chemical formula 15]
Figure BDA0003506505710000231
In the formula (b1-I), R11Represents a hydrogen atom or a methyl group, R12Represents an optionally substituted 2-valent hydrocarbon group, k represents 1 or 2, and represents a bonding arm. The benzene ring in the formula (b1-I) may be further substituted with an arbitrary substituent.
(R12)
In the above formula (b1-I), R12Represents a 2-valent hydrocarbon group optionally having a substituent.
As the 2-valent hydrocarbon group, there may be mentioned: a group in which a 2-valent aliphatic group, a 2-valent aromatic group, and 1 or more 2-valent aliphatic groups are linked to 1 or more 2-valent aromatic groups.
Examples of the aliphatic group having a valence of 2 include linear, branched and cyclic groups. Among these, from the viewpoint of developing solubility, a linear 2-valent aliphatic group is preferable. On the other hand, a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
Examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferred from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include those having, as a side chain, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group on the linear aliphatic group having a valence of 2 described above.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, the number of the cells is preferably 1 to 12, more preferably 1 to 10, and further preferably 2 to 10. When the lower limit value is set to be equal to or higher than the lower limit value, the adhesion between the film and the substrate becomes strong, and when the upper limit value is set to be equal to or lower than the lower limit value, the deterioration of sensitivity, the decrease of the film during development, and the improvement of resolution tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring, a cyclododecane ring, a dicyclopentadiene ring or a dicyclopentane ring. Among these groups, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the aromatic ring group having a valence of 2 include an aromatic ring group having a valence of 2 and an aromatic heterocyclic group having a valence of 2. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, the amount of the surfactant is preferably 4 to 20, more preferably 5 to 15, and still more preferably 6 to 10. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene ring, or aromatic ring,
Figure BDA0003506505710000241
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.
The aromatic heterocyclic ring in the 2-valent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Figure BDA0003506505710000242
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0003506505710000251
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a pyridine ring, a triazine ring, a quinoline ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a pyrimidine ring, a triazine ring, a derivative,
Figure BDA0003506505710000252
Pyridine ring, quinazoline ring, quinazolinone ring, azulene ring.
Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally having a 2-valent aromatic ring group include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. Among these, from the viewpoint of developing solubility, the compound is preferably unsubstituted.
Examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic ring groups having a valence of 2 include groups in which 1 or more of the above-mentioned aliphatic groups having a valence of 2 are linked to 1 or more of the above-mentioned aromatic ring groups having a valence of 2.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
The number of the aromatic ring groups having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
Examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the following formulae (b1-I-A) to (b 1-I-F). Among these, the group represented by the following formula (b1-I-A) is preferable from the viewpoint of rigidity of the skeleton and hydrophobization of the film.
[ chemical formula 16]
Figure BDA0003506505710000261
k represents 1 or 2, preferably 1 from the viewpoint of adhesion and patterning, and preferably 2 from the viewpoint of NMP resistance. The (b1-I) epoxy (meth) acrylate may contain both a partial structure in which k is 1 and a partial structure in which k is 2.
As mentioned above, the benzene ring in the formula (b1-I) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable.
From the viewpoint of ease of synthesis, the partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b 1-I-1).
[ chemical formula 17]
Figure BDA0003506505710000271
In the formula (b1-I-1), R11、R12And k is as defined above for formula (b1-I), RXRepresents a hydrogen atom or a polybasic acid residue, and represents a bonding arm. The benzene ring in the formula (b1-I-1) may be further substituted with an optional substituent.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
As described above, the benzene ring in the formula (b1-I-1) is optionally further substituted with an optional substituent. As the substituent, those exemplified for the benzene ring in the formula (b1-I) can be preferably employed.
The partial structure represented by the formula (b1-I-1) contained in the 1-molecule (b1-I) epoxy (meth) acrylate resin may be one or 2 or more, and R may be present in combinationXIs a hydrogen atom and RXIs a polybasic acid residue.
The number of partial structures represented by the formula (b1-I) contained in the 1-molecule (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less. Preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 15. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
(b1-I) the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, further preferably 3000 or more, particularly preferably 4000 or more, most preferably 5000 or more, and further preferably 30000 or less, more preferably 20000 or less, further preferably 10000 or less, and particularly preferably 8000 or less. For example, the amount of the inorganic filler is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 1500 to 10000, further preferably 1500 to 8000, further preferably 2000 to 8000, and particularly preferably 2000 to 7000. When the lower limit value is not less than the lower limit value, the residual film ratio of the photosensitive coloring composition tends to be good, and when the upper limit value is not more than the upper limit value, the resolution tends to be good.
The acid value of the (b1-I) epoxy (meth) acrylate resin is not particularly limited, but is preferably not less than 10mgKOH/g, more preferably not less than 20mgKOH/g, still more preferably not less than 40mgKOH/g, yet more preferably not less than 50mgKOH/g, and particularly preferably not less than 80mgKOH/g, and further preferably not more than 200mgKOH/g, more preferably not more than 150mgKOH/g, still more preferably not more than 130mgKOH/g, and particularly preferably not more than 100 mgKOH/g. For example, it is preferably from 10mgKOH/g to 200mgKOH/g, more preferably from 20mgKOH/g to 200mgKOH/g, still more preferably from 40mgKOH/g to 150mgKOH/g, yet more preferably from 50mgKOH/g to 130mgKOH/g, and particularly preferably from 80mgKOH/g to 100mgKOH/g or less. When the lower limit value is not less than the above-mentioned lower limit value, the developing solubility tends to be improved and the resolution tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the residual film ratio of the photosensitive coloring composition tends to be good.
Specific examples of the (b1-I) epoxy (meth) acrylate resin are given below, and in the examples, the bond arm is indicated.
[ chemical formula 18]
Figure BDA0003506505710000291
[ chemical formula 19]
Figure BDA0003506505710000292
[ chemical formula 20]
Figure BDA0003506505710000293
[ chemical formula 21]
Figure BDA0003506505710000301
< (b1-II) epoxy (meth) acrylate resin
Next, the epoxy (meth) acrylate resin having a partial structure represented by the general formula (b1-II) will be described in detail.
[ chemical formula 22]
Figure BDA0003506505710000302
In the formula (b1-II), R13Each independently represents a hydrogen atom or a methyl group, R14Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R15And R16Each independently represents a 2-valent aliphatic group optionally having a substituent, m and n each independently represent an integer of 0 to 2, and x represents a bonding arm.
(R14)
In the above general formula (b1-II), R14Represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. For example, the amount of the organic solvent is preferably 4 to 40, more preferably 4 to 30, still more preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
Examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of the residual film ratio and the resolution of the photosensitive coloring composition.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 3 or more, and is usually 10 or less, preferably 5 or less, and more preferably 4 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 4, further preferably 2 to 4, and particularly preferably 3 to 4. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 40, more preferably 6 to 40, further preferably 8 to 30, further preferably 10 to 20, and particularly preferably 12 to 15. When the lower limit is not less than the above-mentioned lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-mentioned upper limit, patterning characteristics tend to be good.
Examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,
Figure BDA0003506505710000311
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.
In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Among these, from the viewpoint of developing solubility, a linear 2-valent aliphatic group is preferable. On the other hand, a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and further preferably 15 or less. For example, the amount of the surfactant is preferably 1 to 25, more preferably 3 to 20, and still more preferably 6 to 15. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
Examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferred from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include those having a structure having a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group as a side chain on the linear aliphatic group having a valence of 2 described above.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to be equal to or higher than the lower limit value, the adhesion between the film and the substrate becomes strong, and when the upper limit value is set to be equal to or lower than the lower limit value, the deterioration of sensitivity, the decrease of the film during development, and the improvement of resolution tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from the ring of a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these groups, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Examples of the aromatic ring group having a valence of 2 include an aromatic ring group having a valence of 2 and an aromatic heterocyclic group having a valence of 2. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene ring, or aromatic ring,
Figure BDA0003506505710000331
A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,
Figure BDA0003506505710000332
A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring
Figure BDA0003506505710000333
An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, a benzimidazole ring, a pyridine ring, a compound, a,
Figure BDA0003506505710000334
Pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally having a 2-valent aromatic ring group include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. Among these, from the viewpoint of developing solubility, the compound is preferably unsubstituted.
Examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic ring groups having a valence of 2 include groups in which 1 or more of the above-mentioned aliphatic groups having a valence of 2 are linked to 1 or more of the above-mentioned aromatic ring groups having a valence of 2.
The number of the 2-valent aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
The number of the aromatic ring groups having a valence of 2 is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
Examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the above-mentioned formulae (b1-I-A) to (b 1-I-F). Among these, the group represented by the formula (b1-I-C) is preferable from the viewpoint of rigidity of the skeleton and hydrophobization of the film.
The bonding mode of the cyclic hydrocarbon group as the side chain is not particularly limited to these 2-valent hydrocarbon groups, and examples thereof include: examples of the aliphatic group and the aromatic ring group include a mode in which 1 hydrogen atom is substituted with a cyclic hydrocarbon group as a side chain and a mode in which 1 carbon atom of the aliphatic group is included to constitute a cyclic hydrocarbon group as a side chain.
(R15、R16)
In the above general formula (b1-II), R15And R16Each independently represents an optionally substituted aliphatic group having a valence of 2.
Examples of the aliphatic group having a valence of 2 include linear, branched and cyclic groups. Among these, from the viewpoint of developing solubility, a linear 2-valent aliphatic group is preferable. On the other hand, a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. For example, the amount of the surfactant is preferably 1 to 20, more preferably 3 to 15, and still more preferably 6 to 10. When the lower limit value is set to the value not less than the upper limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be suppressed easily.
Examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene. Among these, methylene is preferred from the viewpoint of rigidity of the skeleton.
Examples of the branched aliphatic group having a valence of 2 include those having, as a side chain, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group on the linear aliphatic group having a valence of 2 described above.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, the number of the cells is preferably 1 to 12, more preferably 2 to 10. When the lower limit value is set to be equal to or higher than the lower limit value, the adhesion between the film and the substrate becomes strong, and when the upper limit value is set to be equal to or lower than the lower limit value, the deterioration of sensitivity, the decrease of the film during development, and the improvement of resolution tend to be easily suppressed.
Examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring, a cyclododecane ring, or a dicyclopentadiene ring. Among these groups, from the viewpoint of rigidity of the skeleton, a group obtained by removing 2 hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
Examples of the substituent optionally having a 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
(m、n)
In the general formula (b1-II), m and n each independently represent an integer of 0 to 2. When the lower limit value is set to the upper limit value or more, the patterning property tends to be good and surface roughness is less likely to occur, and when the upper limit value is set to the lower limit value or less, the developability tends to be good. From the viewpoint of developability, m and n are preferably 0, and from the viewpoint of patterning characteristics and surface roughness, m and n are preferably 1 or more.
From the viewpoint of adhesion to a substrate, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b 1-II-1).
[ chemical formula 23]
Figure BDA0003506505710000351
In the formula (b1-II-1), R13、R15、R16M and n are as defined above for formula (b1-II), RαRepresents an optionally substituted 1-valent cyclic hydrocarbon group, p represents an integer of 1 or more, and represents a bonding arm. The benzene ring in the formula (b1-II-1) may be further substituted with an optional substituent.
(Rα)
In the above general formula (b1-II-1), RαRepresents an optionally substituted 1-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. For example, the number of the cells is preferably 1 to 6, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 2 to 3. When the lower limit is not less than the above-mentioned lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-mentioned upper limit, patterning characteristics tend to be good.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. Preferably 4 to 40, more preferably 4 to 30, further preferably 6 to 20, and particularly preferably 8 to 15. When the lower limit is not less than the above-mentioned lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-mentioned upper limit, patterning characteristics tend to be good.
Examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.
The number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. When the lower limit is not less than the above-mentioned lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-mentioned upper limit, patterning characteristics tend to be good.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and further preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15. When the lower limit is not less than the above-mentioned lower limit, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit is not more than the above-mentioned upper limit, patterning characteristics tend to be good.
Examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring. Among these, the fluorene ring is preferable from the viewpoint of developing solubility.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, it is preferably 1 to 3, more preferably 2 to 3. When the lower limit value is not less than the above-mentioned lower limit value, the film curing degree and the residual film ratio tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the developing property tends to be good.
Of these, R is preferable from the viewpoint of a strong film curing degreeαIs a 1-valent aliphatic ring group, and is more preferably an adamantyl group.
As described above, the benzene ring in the formula (b1-II-1) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable.
Specific examples of the partial structure represented by the above formula (b1-II-1) are shown below.
[ chemical formula 24]
Figure BDA0003506505710000371
[ chemical formula 25]
Figure BDA0003506505710000372
[ chemical formula 26]
Figure BDA0003506505710000373
[ chemical formula 27]
Figure BDA0003506505710000374
[ chemical formula 28]
Figure BDA0003506505710000375
From the viewpoint of rigidity of the skeleton and hydrophobization of the film, the partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b 1-II-2).
[ chemical formula 29]
Figure BDA0003506505710000381
In the formula (b1-II-2), R13、R15、R16M and n are as defined above for formula (b1-II), RβRepresents a 2-valent cyclic hydrocarbon group optionally having a substituent, and represents a bonding arm. The benzene ring in the formula (b1-II-2) may be further substituted with an optional substituent.
(Rβ)
In the above formula (b1-II-2), RβRepresents an optionally substituted 2-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
The number of rings of the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. For example, it is preferably 1 to 10, more preferably 2 to 5. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. For example, the concentration is preferably 4 to 40, more preferably 6 to 35, and further preferably 8 to 30. When the lower limit value is set to be equal to or higher than the lower limit value, film roughness during development tends to be suppressed, and when the upper limit value is set to be equal to or lower than the lower limit value, deterioration of sensitivity, reduction of film during development, and improvement of resolution tend to be easily suppressed.
Examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isoborneol ring, adamantane ring, cyclododecane ring. Among these, an adamantane ring is preferable from the viewpoint of film reduction and resolution at the time of development.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. For example, the number of the cells is preferably 1 to 10, more preferably 1 to 5, further preferably 2 to 5, and particularly preferably 3 to 5. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. For example, the amount of the surfactant is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
Examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; a carboxyl group. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.
Among these, R is preferable from the viewpoint of suppressing film reduction and resolutionβIs a 2-valent aliphatic ring group, and more preferably a 2-valent adamantyl ring group.
On the other hand, from the viewpoint of patterning characteristics, R is preferableβIs a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in the formula (b1-II-2) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy. The number of the substituents is also not particularly limited, and may be 1 or 2 or more.
Further, 2 benzene rings may be bonded together via a substituent. The substituents in this case include-O-, -S-, -NH-, -CH2An equivalent 2-valent radical.
Among these, from the viewpoint of patterning characteristics, non-substitution is preferable. In addition, methyl substitution is preferable from the viewpoint of less tendency to cause film reduction or the like.
Specific examples of the partial structure represented by the formula (b1-II-2) are shown below, and in the examples, the bond arm is shown.
[ chemical formula 30]
Figure BDA0003506505710000401
[ chemical formula 31]
Figure BDA0003506505710000402
[ chemical formula 32]
Figure BDA0003506505710000403
[ chemical formula 33]
Figure BDA0003506505710000404
The partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoints of the residual film ratio of the coating film and the patterning property.
[ chemical formula 34]
Figure BDA0003506505710000405
In the formula (b1-II-3), R13、R14、R15、R16M and n are as defined above for formula (b1-II), RZRepresents a hydrogen atom or a polybasic acid residue.
The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid. Furthermore, 1 OH group may be removed and R in another molecule represented by the formula (b1-II-3)ZIn common, i.e. via RZA plurality of the formula (b1-II-3) are linked together.
Examples of the polybasic acid include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexachloronorbornenedioic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.
The partial structure represented by the formula (b1-II-3) contained in 1 molecule of (b1-II) epoxy (meth) acrylate resin may be one or 2 or more, and R may be present in combinationZIs a hydrogen atom and RZIs a polybasic acid residue.
The number of partial structures represented by the formula (b1-II) contained in the 1-molecule (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and further preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. For example, the number of the cells is preferably 1 to 20, more preferably 1 to 15, and further preferably 3 to 10. When the lower limit value is set to the value not less than the lower limit value, a strong film is easily obtained and surface roughness is less likely to occur, and when the upper limit value is set to the value not more than the upper limit value, deterioration of sensitivity, reduction of the film at the time of development, and improvement of resolution tend to be easily suppressed.
(b1-II) the weight average molecular weight (Mw) of the epoxy (meth) acrylate resin in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, and further preferably 20000 or less, more preferably 10000 or less, further preferably 7000 or less, and particularly preferably 5000 or less. For example, it is preferably 1000 to 30000, more preferably 1000 to 20000, further preferably 1000 to 10000, further preferably 2000 to 7000, and particularly preferably 2000 to 5000. When the lower limit value is set to the value not less than the lower limit value, patterning characteristics tend to be good, and when the upper limit value is set to the value not more than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur.
The acid value of the (b1-II) epoxy (meth) acrylate resin is not particularly limited, but is preferably not less than 10mgKOH/g, more preferably not less than 20mgKOH/g, still more preferably not less than 40mgKOH/g, yet more preferably not less than 60mgKOH/g, particularly preferably not less than 80mgKOH/g, most preferably not less than 100mgKOH/g, and further preferably not more than 200mgKOH/g, more preferably not more than 150mgKOH/g, and still more preferably not more than 120 mgKOH/g. For example, it is preferably from 10mgKOH/g to 200mgKOH/g, more preferably from 20mgKOH/g to 200mgKOH/g, still more preferably from 40mgKOH/g to 150mgKOH/g, yet more preferably from 60mgKOH/g to 150mgKOH/g, yet more preferably from 80mgKOH/g to 120mgKOH/g, and particularly preferably from 100mgKOH/g to 120 mgKOH/g. When the lower limit value is not less than the above-mentioned lower limit value, a strong film tends to be easily obtained, and when the upper limit value is not more than the above-mentioned upper limit value, the developing solubility tends to be improved and the resolution tends to be good.
The carboxyl group-containing epoxy (meth) acrylate resin may be used alone or in combination with 2 or more kinds of resins.
In addition, a part of the above-mentioned 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, still more preferably 80% by mass or more, and usually 100% by mass or less.
In addition, as the alkali-soluble resin (b), acrylic copolymer resin (b2) is preferably used from the viewpoint of compatibility with pigments, dispersants, and the like, and those described in Japanese patent application laid-open No. 2014-137466 can be preferably used.
Examples of the acrylic copolymer resin include: a copolymer of an ethylenically unsaturated monomer having 1 or more carboxyl groups (hereinafter, referred to as "unsaturated monomer (b 2-1)") and another ethylenically unsaturated monomer copolymerizable therewith (hereinafter, referred to as "unsaturated monomer (b 2-2)").
Examples of the unsaturated monomer (b2-1) include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic anhydride, and mesaconic acid; mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polybasic 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-vinyl benzoic acid.
These unsaturated monomers (b2-1) may be used alone or in combination of 2 or more.
Examples of the unsaturated monomer (b2-2) include:
n-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
aromatic vinyl compounds such as styrene, α -methylstyrene, p-hydroxystyrene, p-hydroxy- α -methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthene;
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, and tricyclo [5.2.1.0 ] meth) acrylate2,6]Decane-8-yl ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of thymol, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 3- [ (meth) acryloyloxymethyl]Oxygen oxideCyclobutane, 3- [ (meth) acryloyloxymethyl](meth) acrylates of 3-ethyloxetane and the like;
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;
a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain of polystyrene, poly (methyl (meth) acrylate), poly (n-butyl (meth) acrylate), polysiloxane, or the like.
These unsaturated monomers (b2-2) may be used alone or in combination of 2 or more.
In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the unsaturated monomer (b2-1) is copolymerized in such a range, a photosensitive coloring composition having excellent alkali developability and storage stability tends to be obtained.
Examples of the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) include copolymers disclosed in, for example, Japanese patent application laid-open Nos. 7-140654, 8-259876, 10-31308, 10-300922, 11-174224, 11-258415, 2000-56118 and 2004-101728.
The copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2) can be produced by a known method, or 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 and 2007/029871.
Further, the resins disclosed in International publication No. 2016/194619 and International publication No. 2017/154439 may be used.
< (c) photopolymerization initiator
(c) The photopolymerization initiator is a component having a function of directly absorbing light to cause a decomposition reaction or a hydrogen abstraction reaction to generate 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 Japanese patent 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 BDA0003506505710000441
Oxadiazole derivatives, halomethyl s-triazine derivatives, and alpha-aminoalkylphenone derivatives; oxime ester compounds described in, for example, Japanese patent application laid-open Nos. 2000-80068 and 2006-36750.
Examples of the metallocene compound include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5, 6-pentafluoro-1-yl) titanium, dicyclopentadienyl bis (2,3,5, 6-tetrafluoro-1-yl) titanium, dicyclopentadienyl bis (2,4, 6-trifluoro-1-yl) titanium, dicyclopentadienyl bis (2, 6-difluorophen-1-yl) titanium, dicyclopentadienyl bis (2, 4-difluorophen-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophen-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophen-1-yl) titanium, dicyclopentadienyl [2, 6-difluoro-3- (1-propyl) phen-1-yl ] titanium.
Examples of the hexaarylbiimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, and (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer.
As halomethylation
Figure BDA0003506505710000442
Oxadiazole derivatives, for example: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-
Figure BDA0003506505710000443
Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-
Figure BDA0003506505710000444
Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-
Figure BDA0003506505710000445
Diazole, 2-trichloromethyl-5-furyl-1, 3,4-
Figure BDA0003506505710000446
Diazole.
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.
Examples of α -aminoalkylphenone derivatives include: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 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.
The oxime ester compounds are effective as photopolymerization initiators in particular from the viewpoint of sensitivity and platemaking property, and, for example, when an alkali-soluble resin containing a phenolic hydroxyl group is used, such an oxime ester compound having excellent sensitivity is particularly useful. The oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in combination in its structure, and therefore, it is highly sensitive even in a small amount, stable against thermal reaction, and it is possible to obtain a photosensitive coloring composition having high sensitivity in a small amount.
Examples of the oxime ester compounds include compounds represented by the following general formula (IV).
[ chemical formula 35]
Figure BDA0003506505710000451
In the above formula (IV), R21aRepresents a hydrogen atom, an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.
R21bRepresents an optional substituent containing an aromatic ring.
R22aRepresents an alkanoyl group optionally having a substituent, or an aroyl group optionally having a substituent.
n represents an integer of 0 or 1.
R21aThe number of carbon atoms of the alkyl group in (b) is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, and more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Specific examples of the alkyl group include: methyl, ethyl, propyl, cyclopentylethyl.
Examples of the substituent optionally contained in the alkyl group include: an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, a 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl group or an N-acetyl-N-acetoxyamino group, is preferably unsubstituted from the viewpoint of ease of synthesis.
As R21aAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, and is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. From the viewpoint of developability, the amount is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
Examples of the aromatic ring group include: of these, phenyl, naphthyl, pyridyl and furyl are preferable, and phenyl or naphthyl is more preferable, and phenyl is even more preferable, from the viewpoint of developability.
Examples of the substituent optionally contained in the aromatic ring group include: the hydroxyl group, the carboxyl group, the halogen atom, the amino group, the amide group, the alkyl group, the alkoxy group, and the group in which these substituents are linked together are preferably an alkyl group, an alkoxy group, and a group in which these substituents are linked together, and more preferably a linked alkoxy group, from the viewpoint of developability.
Among these, R is R from the viewpoint of developability21aPreferred is an aromatic ring group optionally having a substituent, and more preferred is an aromatic ring group having a substituent with an attached alkoxy group.
In addition, as R21bExamples thereof include optionally substituted carbazolyl groups, optionally substituted thioxanthone groups, and optionally substituted diphenylsulfide groups. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity, and an optionally substituted diphenylsulfide group is preferable from the viewpoint of electrical reliability.
In addition, R22aThe number of carbon atoms of the alkanoyl group in (b) is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less, from the viewpoint of solubility in a solvent and sensitivity. Examples of alkanoyl groups include: acetyl, propionyl and butyryl.
Examples of the substituent optionally contained in the alkanoyl group include: the aromatic ring group, hydroxyl group, carboxyl group, halogen atom, amino group, and amide group are preferably unsubstituted from the viewpoint of ease of synthesis.
In addition, R22aThe number of carbon atoms of the aroyl group in (2) is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solubility in a solvent and sensitivity. Examples of the aroyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent optionally contained in the aroyl group include: the hydroxyl group, the carboxyl group, the halogen atom, the amino group, the amide group, and the alkyl group are preferably unsubstituted from the viewpoint of ease of synthesis.
Of these, R is from the viewpoint of sensitivity22aPreferred is an alkanoyl group optionally having a substituent, more preferred is an unsubstituted alkanoyl group, and further preferred is an acetyl group.
From the viewpoint of reducing contamination of the liquid crystal layer by the colorant, it is also preferable to use the initiator described in Japanese patent laid-open publication No. 2016-133574.
The photopolymerization initiator may be used alone or in combination of 2 or more.
For the purpose of improving the sensitivity, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended as necessary with the photopolymerization initiator. Examples of the sensitizing dye include: japanese patent laid-open Nos. 4-221958 and 4-219756
Figure BDA0003506505710000471
Xanthene dye, coumarin dye having a heterocycle as described in Japanese patent application laid-open Nos. 3-239703 and 5-289335, 3-oxocoumarin compound as described in Japanese patent application laid-open Nos. 3-239703 and 5-289335, methylene pyrrole dye as described in Japanese patent application laid-open No. 6-19240, Japanese patent application laid-open Nos. 47-2528, 54-155292, 45-37377, 48-84183, 52-112681, 58-15503, 60-88005, 59-56403, 2-69, 57-168088, 5-107761, Dyes having a dialkylaminophenyl skeleton as described in Japanese patent laid-open Nos. 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. Preference is given, for example: 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenoneBenzophenone compounds such as ketone, 4-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzo
Figure BDA0003506505710000472
Azole, 2- (p-diethylaminophenyl) benzo
Figure BDA0003506505710000473
Azole, 2- (p-dimethylaminophenyl) benzo [4, 5]]Benzo (b) is
Figure BDA0003506505710000474
Azole, 2- (p-dimethylaminophenyl) benzo [6, 7]]Benzo (b) is
Figure BDA0003506505710000475
Oxazole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-
Figure BDA0003506505710000476
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, (p-diethylaminophenyl) pyrimidine, and the like, and 4, 4' -dialkylaminobenzophenone is particularly preferable.
The sensitizing pigment can be used singly or in combination of 2 or more
As the polymerization accelerator, for example, 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 can be used. The polymerization accelerator may be used singly or in combination of 2 or more.
< (d) an ethylenically unsaturated compound
The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound, and the sensitivity is improved by containing (d) an ethylenically unsaturated compound.
The ethylenically unsaturated compound used in the present invention is a compound having at least 1 ethylenically unsaturated group in the molecule. Specifically, for example: monoesters of (meth) acrylic acid, alkyl (meth) acrylates, acrylonitrile, styrene, and carboxylic acids having 1 ethylenically unsaturated bond with 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 contained in 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. For example, the number of the cells is preferably 2 to 8, more preferably 2 to 7, further preferably 4 to 7, and particularly preferably 5 to 7. When the lower limit value is not less than the lower limit value, the sensitivity tends to be high, and when the upper limit value is not more than the upper limit value, the solubility in a solvent tends to be improved.
As examples of polyfunctional olefinic monomers, mention may be made, for example, of: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyol such as an aliphatic polyol or an aromatic polyol with an unsaturated carboxylic acid or a polycarboxylic acid.
Examples of the ester of an aliphatic polyhydric compound and an unsaturated carboxylic acid include: acrylic 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 esters obtained by replacing these acrylic esters with methacrylic esters, itaconic esters obtained by replacing these acrylic esters with itaconic esters, crotonic esters obtained by replacing these with crotonic esters, and maleic esters obtained by replacing these with maleic esters.
Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include: acrylate and methacrylate of aromatic polyhydroxy compound such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, 1,2, 3-benzenetriol triacrylate, etc.
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 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.
Further, examples of the polyfunctional ethylenic monomer used in the present invention include 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 are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ningmura chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyowa Kagaku Co., Ltd.), UV-1700B, UV-7600B, UV-7656 7605B, UV-7630B, UV7640 357640 7640B (manufactured by Nippon Kagaku Co., Ltd.).
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 contains (e) a solvent, and by containing (e) a solvent, the colorant (a) can be dispersed or dissolved in the solvent, and the coating can be facilitated.
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, an organic solvent having a boiling point of 100 to 300 ℃ is preferably selected, and an organic solvent having a boiling point of 120 to 280 ℃ is more preferably selected. The boiling point as used herein means a boiling point at a pressure of 1013.25hPa, and the boiling points are the same as below.
Examples of such organic solvents include:
glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;
glycol diacetate esters such as ethylene glycol diacetate, 1, 3-butanediol diacetate, and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexyl acetate;
ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and 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.
As commercially available organic solvents, for example: mineral spirits (Mineral spirits), Varsol #2, Apco #18solvent, Apco trinner, Socal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve" is a registered trademark, the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all of which are trade names).
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, the organic solvent is preferably selected to have a boiling point of 100 to 200 ℃, and more preferably 120 to 170 ℃.
Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coatability, surface tension, and the like, and high solubility of the constituent components in the composition.
In addition, the glycol alkyl ether acetates may be used alone or in combination with other organic solvents. The organic solvent used in combination is particularly preferably a glycol monoalkyl ether. Among these, propylene glycol monomethyl ether is preferred in particular from the viewpoint of solubility of the constituent components in the composition. The glycol monoalkylethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate easily, and the storage stability of the photosensitive coloring composition obtained thereafter tends to be lowered, for example, the viscosity of the composition increases, and therefore the proportion of the glycol monoalkylethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
In addition, it is also preferably used in combination with an organic solvent having a boiling point of 150 ℃ or higher (hereinafter, sometimes referred to as "high-boiling solvent"). When the pigment is used in combination with such a high boiling point solvent, the photosensitive coloring composition is difficult to dry, but the pigment is prevented from being broken in a uniform dispersion state in the composition in the case of rapid drying. That is, for example, the effect of preventing the occurrence of foreign matter defects at the tip of the slit nozzle due to precipitation and solidification of a colorant or the like is obtained. Among the various solvents, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol mono-ethyl ether acetate are particularly preferable from the viewpoint of high effects.
When a high-boiling solvent is used in combination, the content of the high-boiling solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. By setting the lower limit value or more, it is possible to suppress the occurrence of a foreign matter defect at the tip of the slit nozzle due to precipitation and solidification of a color material or the like, for example, and by setting the upper limit value or less, it is possible to suppress the drying rate of the composition from being lowered, and there is a tendency that it is possible to suppress a problem such as a tact failure in the reduced pressure drying process or a pin mark in the pre-bake (pre-cake).
The high boiling point solvent having a boiling point of 150 ℃ or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
Preferred high boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol mono-ethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin among the above solvents.
(f) dispersant
The photosensitive coloring composition of the present invention contains (f) a dispersant, and by containing (f) a dispersant, the colorant (a) can be stably dispersed.
The dispersant (f) in the photosensitive coloring composition of the present invention contains a dispersant (f1) (hereinafter, may be referred to as "dispersant (f 1)") having a repeating unit represented by the following general formula (1).
[ chemical formula 36]
Figure BDA0003506505710000521
(in the formula (1), R1～R3Each independently is an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, R1～R32 or more of them may be bonded to each other to form a ring structure.
R4Is a hydrogen atom or a methyl group.
X is a linking group having a valence of 2.
Y-Is a counter anion represented by the following general formula (2). )
[ chemical formula 37]
Figure BDA0003506505710000522
(in the formula (2), R5Is an alkyl group optionally having a substituent. )
The dispersant (f1) is a dispersant having an ammonium group and a counter anion of an alkylsulfonic acid ion. The alkylsulfonic acid ion is stably bonded to the ammonium group as an anion derived from the ester. Therefore, it is presumed that the dispersant is not easily released from the colorant but is stable even when immersed in an amine solvent such as N-methylpyrrolidone (NMP), the dispersant is kept in a state of adsorbing and covering the surface of the colorant, and a part of the colorant is rarely eluted as impurities.
On the other hand, since the counter anion of the general formula (2) is stably bonded to an ammonium group as a sulfonic acid ion derived from an ester, it is considered that when an excessive dispersant not adsorbed to a pigment remains in a cured product, the dispersant is formed into a sulfonic acid ion and is not easily released into a liquid crystal, and therefore, the counter anion is not easily affected by the alignment property of the liquid crystal, and thus, the voltage holding ratio is not easily lowered. It is presumed that the polymer is not easily released particularly after ultraviolet irradiation and the voltage holding ratio is not easily lowered.
(R1～R3)
In the above formula (1), R1～R3Each independently is an alkyl group optionally having a substituent, or an aryl group optionally having a substituent.
As R1～R3The alkyl group in (b) may be a linear, branched or cyclic alkyl group, and is preferably linear from the viewpoint of voltage holding ratio after ultraviolet irradiation and NMP resistance.
The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 6 or less, further preferably 2 or less, and usually 1 or more. When the amount is equal to or less than the upper limit, the dispersion tends to have good stability with time.
Examples of the alkyl group include: the methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of the stability of the dispersion over time.
Examples of the substituent optionally contained in the alkyl group include: alkoxy groups such as methoxy and ethoxy; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc.; aralkyl groups such as benzyl and phenethyl; aryl groups such as phenyl and naphthyl groups are preferably unsubstituted from the viewpoint of dispersibility.
As R1～R3Examples of the aryl group in (1) include an aromatic hydrocarbon ring group having a valence of 1 and an aromatic heterocyclic group having a valence of 1.
The number of carbon atoms of the aryl group is not particularly limited, but is preferably 24 or less, more preferably 18 or less, further preferably 12 or less, and usually 6 or more. When the amount is equal to or less than the upper limit, the dispersibility tends to be improved.
Examples of the aryl group include: the phenyl group, naphthyl group and anthracenyl group are preferably a phenyl group or naphthyl group, and more preferably a phenyl group, from the viewpoint of dispersibility.
Examples of the substituent optionally contained in the aryl group include: alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc.; aralkyl groups such as benzyl and phenethyl are preferably unsubstituted from the viewpoint of dispersibility.
In the above formula (1), R1～R32 or more of them may be bonded to each other to form a ring structure, and examples of the ring structure include: a 5-7 membered ring nitrogen-containing heterocyclic monocyclic ring, or a condensed ring obtained by condensing 2 of the nitrogen-containing heterocyclic monocyclic rings. The nitrogen-containing heterocyclic monocyclic ring preferably has no aromaticity, and more preferably is a saturated ring. Specific examples thereof include the following ring structures.
[ chemical formula 38]
Figure BDA0003506505710000541
(in the above formula, R is R1～R3Any of the above. In addition, these cyclic structures may further have a substituent, which represents a bonding arm. )
Among these, R is preferable from the viewpoint of the voltage holding ratio after ultraviolet irradiation and the NMP resistance1～R3Each independently is an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
(X)
In the formula (1), X is a linking group having a valence of 2.
Examples of the linking group having a valence of 2 include: a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R6-radical, -COOR7-radical (wherein, R6And R7Independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkoxyalkyl) having 2 to 10 carbon atoms), preferably-COOR from the viewpoint of dispersibility7-a radical. R7Among them, from the viewpoint of the stability of the dispersion over time, it is preferably C1EThe alkylene group of 10 is more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms.
(Y-)
In the above formula (1), Y-Is a counter anion represented by the following general formula (2).
[ chemical formula 39]
Figure BDA0003506505710000542
(in the formula (2), R5Is an alkyl group optionally having a substituent. )
(R5)
As R5Examples of the alkyl group in (b) include a linear, branched, or cyclic alkyl group, and a linear alkyl group is preferable from the viewpoint of voltage retention after ultraviolet irradiation.
The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 6 or less, more preferably 4 or less, further preferably 2 or less, and usually 1 or more. When the value is equal to or less than the upper limit, the voltage holding ratio after the ultraviolet irradiation tends to be high. Examples of the alkyl group include: the methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of the voltage holding ratio after ultraviolet irradiation.
Examples of the substituent optionally contained in the alkyl group include: alkoxy groups such as methoxy and ethoxy; halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms are preferably unsubstituted from the viewpoint of the voltage holding ratio after ultraviolet irradiation.
Of these, R is preferable from the viewpoint of voltage holding ratio after ultraviolet irradiation5The unsubstituted alkyl group is more preferably a methyl group or an ethyl group, and still more preferably a methyl group.
The dispersant (f1) has the repeating unit represented by the general formula (1) above, and may further have another repeating unit.
From the viewpoint of the voltage holding ratio before and after ultraviolet irradiation, the dispersant (f1) preferably has a repeating unit represented by the following general formula (3).
[ chemical formula 40]
Figure BDA0003506505710000551
(in the formula (3), R8And R9Each independently is an alkyl group optionally having a substituent, or an aryl group optionally having a substituent, R8And R9May be bonded to each other to form a ring structure.
R10Is a hydrogen atom or a methyl group.
Z is a linking group having a valence of 2. )
In the above formula (3), R8And R9Each independently is an alkyl group optionally having a substituent, or an aryl group optionally having a substituent. As the alkyl group optionally having a substituent, the aryl group optionally having a substituent, R in the aforementioned formula (1) can be preferably employed1～R3Those listed.
In the above formula (3), R8And R9May be bonded to each other to form a ring structure. Examples of the cyclic structure include: a 5-7 membered ring nitrogen-containing heterocyclic monocyclic ring, or a condensed ring obtained by condensing 2 of the nitrogen-containing heterocyclic monocyclic rings. The nitrogen-containing heterocyclic monocyclic ring preferably has no aromaticity, and more preferably is a saturated ring. Specific examples thereof include the following ring structures.
[ chemical formula 41]
Figure BDA0003506505710000561
(these cyclic structures may further have a substituent(s); represents a bonding arm.)
In the formula (3), Z is a linking group having a valence of 2. As the linking group having a valence of 2, those exemplified as X in the aforementioned formula (1) can be preferably employed.
In addition, from the viewpoint of improving compatibility with a solvent or an alkali-soluble resin and improving dispersion stability, the dispersant (f1) preferably has a repeating unit represented by the following general formula (4).
[ chemical formula 42]
Figure BDA0003506505710000562
(in the formula (4), R11Is a hydrogen atom, an alkyl group optionally having a substituent, or an aryl group optionally having a substituent.
R12Is a hydrogen atom or a methyl group. )
(R11)
As R11The alkyl group in (b) may be a linear, branched or cyclic alkyl group, and is preferably a linear alkyl group from the viewpoint of compatibility with a solvent or an alkali-soluble resin, and is preferably a branched alkyl group from the viewpoint of affinity for a pigment.
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, and further preferably 6 or less. When the lower limit value is not less than the above-mentioned lower limit value, the affinity for the pigment tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the compatibility with the solvent or the alkali-soluble resin tends to be improved, and the dispersibility tends to be good.
Examples of the alkyl group include: the methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and ethylhexyl group are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
Examples of the substituent optionally contained in the alkyl group include: alkoxy groups such as methoxy and ethoxy; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc.; the aryl group such as a phenyl group or a naphthyl group is preferably unsubstituted from the viewpoint of compatibility with a solvent or an alkali-soluble resin, and is preferably a phenyl group from the viewpoint of affinity with a pigment.
As R11Examples of the aryl group in (1) include an aromatic hydrocarbon ring group having a valence of 1 and an aromatic heterocyclic group having a valence of 1.
The number of carbon atoms of the aryl group is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. When the upper limit value is not more than the above-mentioned upper limit value, the affinity for the pigment tends to be improved. Examples of the aryl group include: the phenyl group, naphthyl group and anthracenyl group are preferably a phenyl group or naphthyl group, and more preferably a phenyl group, from the viewpoint of dispersibility.
Examples of the substituent optionally contained in the aryl group include: alkyl groups such as methyl and ethyl; alkoxy groups such as methoxy and ethoxy; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc.; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl and phenethyl are preferably unsubstituted from the viewpoint of dispersibility.
Among these, from the viewpoint of compatibility with a solvent or an alkali-soluble resin, R is11The alkyl group is preferably an alkyl group optionally having a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group, a butyl group, or an ethylhexyl group.
In addition, from the viewpoint of compatibility with a solvent or an alkali-soluble resin, the dispersant (f1) preferably has a repeating unit represented by the following general formula (5).
[ chemical formula 43]
Figure BDA0003506505710000571
(in the formula (5), R13Is methylene, ethylene, or propylene.
R14Is methyl, ethyl, or propyl.
R15Is a hydrogen atom or a methyl group.
n is an integer of 1 to 20. )
R13The methylene group, the ethylene group, or the propylene group is preferably an ethylene group from the viewpoint of compatibility with a solvent or an alkali-soluble resin.
R14Methyl, ethyl, or propyl, and methyl or ethyl is preferred from the viewpoint of compatibility with a solvent or an alkali-soluble resinEthyl, more preferably ethyl.
n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less. For example, the amount of the surfactant is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 5.
When the lower limit value is not less than the above-mentioned lower limit value, compatibility with a solvent or an alkali-soluble resin tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, affinity with a pigment tends to be improved, and dispersibility tends to be good.
The content ratio of the repeating unit represented by the general formula (1) (hereinafter, may be referred to as "repeating unit (1)") in the dispersant (f1) is not particularly limited, but is preferably 2 mol% or more, more preferably 5 mol% or more, further preferably 7 mol% or more, further preferably 10 mol% or more, and particularly preferably 12 mol% or more, and is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less in all the repeating units. For example, it is preferably 2 to 50 mol%, more preferably 5 to 40 mol%, still more preferably 7 to 30 mol%, still more preferably 7 to 20 mol%, and particularly preferably 7 to 15 mol%. When the lower limit value is not less than the above-mentioned lower limit value, the dispersion tends to have good stability with time, and when the upper limit value is not more than the above-mentioned upper limit value, the dispersion tends to have good dispersibility.
The content of the repeating unit represented by the general formula (3) (hereinafter, may be referred to as "repeating unit (3)") in the dispersant (f1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 12 mol% or more, particularly preferably 15 mol% or more, and further preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and particularly preferably 20 mol% or less in all the repeating units. For example, it is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, still more preferably 12 to 30 mol%, and particularly preferably 15 to 20 mol%. When the lower limit value is not less than the above-mentioned lower limit value, the dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the stability of the dispersion with time tends to be good.
When the dispersant (f1) contains the repeating unit (3), the content of the repeating unit (1) is usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 30 mol% or more with respect to the total of the repeating unit (1) and the repeating unit (3), and is usually 100 mol% or less, preferably 80 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. For example, it is preferably 5 to 100 mol%, more preferably 10 to 80 mol%, still more preferably 20 to 60 mol%, still more preferably 25 to 50 mol%, and particularly preferably 30 to 40 mol%. When the lower limit value is not less than the above-mentioned lower limit value, the voltage holding ratio and NMP resistance after ultraviolet irradiation tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the stability of the dispersion with time tends to be good.
When the dispersant (f1) contains the repeating unit represented by the general formula (4) (hereinafter, may be referred to as "repeating unit (4)"), the content ratio thereof is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, further preferably 50 mol% or more, and particularly preferably 60 mol% or more, and is preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 65 mol% or less, based on all the repeating units. For example, it is preferably 20 to 90 mol%, more preferably 30 to 90 mol%, still more preferably 40 to 80 mol%, still more preferably 50 to 80 mol%, and particularly preferably 60 to 80 mol%. When the lower limit value is not less than the above-mentioned lower limit value, the affinity for the pigment tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the compatibility with the solvent or the alkali-soluble resin tends to be improved.
When the dispersant (f1) contains the repeating unit represented by the general formula (5) (hereinafter, may be referred to as "repeating unit (5)"), the content ratio thereof is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, further preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 15 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less, of all the repeating units. For example, it is preferably 1 to 30 mol%, more preferably 1 to 20 mol%, still more preferably 2 to 15 mol%, still more preferably 2 to 10 mol%, and particularly preferably 3 to 5 mol%. When the lower limit value is not less than the above-mentioned lower limit value, compatibility with a solvent or an alkali-soluble resin tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, affinity with a pigment tends to be improved.
When the dispersant (f1) has the repeating unit (1) and the repeating unit (3), from the viewpoint of dispersibility, it is preferably a block copolymer having a B block having the repeating unit (1) and the repeating unit (3) and an a block having no repeating unit (1) and no repeating unit (3). The block copolymer is preferably an A-B block copolymer or an A-B-A block copolymer.
In the B block, the repeating unit (1) and the repeating unit (3) may be contained in any form of random copolymerization or block copolymerization. In addition, the B block may contain 2 or more kinds of the repeating unit (1) and the repeating unit (3), respectively, and in this case, each repeating unit may be contained in the B block by random copolymerization or block copolymerization.
When the dispersant (f1) has the repeating unit (4) or the repeating unit (5), these may be contained in the a block, and may be contained in any form of random copolymerization or block copolymerization. In addition, the a block may contain 2 or more kinds of the repeating unit (4) and the repeating unit (5), and in this case, each repeating unit may be contained in the a block by random copolymerization or block copolymerization.
The a block may contain a repeating unit other than the repeating units (4) and (5), and examples of such a repeating unit include styrene-based monomers derived from styrene, α -methylstyrene, and the like; (meth) acrylate monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units of N-methacryloylmorpholine.
The amine value of the dispersant (f1) is not particularly limited, but is preferably 20mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 40mgKOH/g or more, and particularly preferably 45mgKOH/g or more, and is preferably 150mgKOH/g or less, more preferably 100mgKOH/g or less, further preferably 80mgKOH/g or less, and particularly preferably 60mgKOH/g or less. For example, it is preferably from 20mgKOH/g to 150mgKOH/g, more preferably from 30mgKOH/g to 100mgKOH/g, still more preferably from 40mgKOH/g to 80mgKOH/g, and particularly preferably from 45mgKOH/g to 60 mgKOH/g. When the lower limit value is not less than the above-mentioned lower limit value, the dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the stability of the dispersion with time tends to be good. The amine number is represented by the mass of KOH corresponding to the amount of the base of 1g of the solid content of the dispersant (f 1).
The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10mgKOH/g or less, more preferably 5mgKOH/g or less, still more preferably 1mgKOH/g or less, and particularly preferably 0 mgKOH/g.
The weight average molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, and even more preferably 7000 or more, and is preferably 100000 or less, more preferably 50000 or less, and even more preferably 10000 or less. For example, it is preferably 3000 to 100000, more preferably 5000 to 50000, and further preferably 7000 to 10000. When the lower limit value is not less than the above-mentioned lower limit value, the dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the stability of the dispersion with time tends to be good.
In addition, in the dispersant of the present invention, Y is a counter anion due to the presence of-In some cases, the weight average molecular weight cannot be sufficiently measured, and in such cases, Y is sometimes added-Theoretical molecular weight calculated from previous weight average molecular weight values.
The theoretical molecular weight of the dispersant (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, and even more preferably 7000 or more, and is preferably 100000 or less, more preferably 50000 or less, and even more preferably 10000 or less. For example, it is preferably 3000 to 100000, more preferably 5000 to 50000, and further preferably 7000 to 10000. When the lower limit value is not less than the above-mentioned lower limit value, the dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the stability of the dispersion with time tends to be good.
The method for producing the dispersant (f1) is not particularly limited, and a known method can be used. For example, the compound represented by the following general formula (2') can be produced by reacting a precursor of the dispersant (f1) containing the repeating unit (3).
[ chemical formula 44]
Figure BDA0003506505710000611
(in the formula (2'), R5R has the same meaning as in the above formula (2)50And R in the above formula (1)1～R3Any of the groups in (a) have the same meaning. )
The dispersant (f) in the photosensitive coloring composition of the present invention may contain a dispersant other than the dispersant (f1) (hereinafter, may be referred to as "other dispersant").
As the other dispersant, for example, a dispersant having a carboxyl group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a dispersant having a functional group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine. Among them, more preferred are those having a basic functional group, for example, having a primary amino group, a secondary amino group or a tertiary amino group; quaternary ammonium salt groups; dispersants derived from nitrogen-containing heterocyclic groups such as pyridine, pyrimidine and pyrazine.
In addition, a polymer dispersant is preferable from the viewpoint that the pigment can be dispersed with a small amount of the dispersant when the pigment is dispersed.
Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising an amino group-containing monomer and a macromonomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
Examples of such a polymer dispersant include those having trade names of EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), DISPARLON (registered trademark, manufactured by Nako chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation, KP (manufactured by shin-Etsu chemical Co., Ltd.), POLYFLOW (manufactured by Kyoho chemical Co., Ltd.), and AJISPER (registered trademark, manufactured by K.K.).
Examples of the urethane and acrylic polymer dispersants include: DISPERBYK 160-166, 182 series (all carbamates), DISPERBYK2000, 2001, BYK-LPN21116 (all acrylics) (all manufactured by BYK-Chemie).
One kind of other dispersant may be used, or 2 or more kinds may be used in combination.
< other compounding ingredients of photosensitive coloring composition >
In addition to the above components, additives such as adhesion improving agents such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors can be suitably blended in the photosensitive coloring composition of the present invention.
(1) Adhesion improver
In order to improve adhesion to a substrate, an adhesion enhancer may be contained in the photosensitive coloring composition of the present invention. The adhesion improver is preferably a silane coupling agent, a compound containing a phosphoric group, or the like.
The silane coupling agent may be 1 kind of epoxy, meth (acrylic), or amino silane coupling agent, or 2 or more kinds of silane coupling agents may be used alone or in combination.
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 preferably 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 45]
Figure BDA0003506505710000631
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 alone or in combination of 2 or more.
(2) Surface active agent
In order to improve coatability, a surfactant may be contained in the photosensitive coloring composition of the present invention.
As the surfactant, various surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. Among them, nonionic surfactants are preferably used from the viewpoint of low possibility of exerting adverse effects on various properties, and among them, fluorine-based and silicone-based surfactants are effective from the viewpoint of coatability.
Examples of such surfactants include: TSF4460 (manufactured by Momentive Performance Materials Co., Ltd.), DFX-18 (manufactured by NEOS Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie Co., Ltd.), KP340 (manufactured by shin-Etsu Silicone Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Co., Ltd.), SH7PA (manufactured by Dow Corning Toray Co., Ltd.), DS-401 (manufactured by Dajin Co., Ltd.), L-77 (manufactured by YOU K.K., Japan), and FC4430 (manufactured by 3M Co., Ltd.).
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, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, bisindanone
Figure BDA0003506505710000641
Azines, anthraquinones, indanthrones, perylenes, perinones, diketopyrrolopyrroles
Figure BDA0003506505710000642
Among the oxazine derivatives, phthalocyanines and quinophthalones are preferable.
Examples of the substituent of the pigment derivative include: sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, and the like, which may be bonded directly or via an alkyl group, aryl group, heterocyclic group, or the like, to the pigment skeleton, and among the substituents of the above pigment derivatives, sulfonic acid groups are preferable. In addition, a plurality of these substituents may be substituted on one pigment skeleton.
Examples of the pigment derivative include: sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, diketopyrrolopyrroleSulfonic acid derivative, bis
Figure BDA0003506505710000643
Sulfonic acid derivatives of oxazines. 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 the photoacid generators, those having high solubility in a solvent, particularly in a solvent used for the photosensitive coloring composition, are preferable. Examples thereof include: diphenyl iodide
Figure BDA0003506505710000647
Dimethyl phenyl iodide
Figure BDA0003506505710000648
Phenyl (p-methoxybenzyl) iodide
Figure BDA0003506505710000649
Bis (m-nitrophenyl) iodide
Figure BDA00035065057100006410
Bis (p-tert-butylphenyl) iodide
Figure BDA00035065057100006411
Bis (p-chlorophenyl) iodide
Figure BDA00035065057100006412
Bis (n-dodecyl) iodide
Figure BDA00035065057100006413
P-isobutylphenyl (p-tolyl) iodide
Figure BDA00035065057100006414
P-isopropylphenyl (p-tolyl) iodide
Figure BDA00035065057100006415
Isodiaryl iodides
Figure BDA00035065057100006416
Chloride, bromide, or borofluoride of triarylsulfonium such as triphenylsulfonium, hexafluorophosphate, hexafluoroarsenite, aromatic sulfonate, and tetrakis (pentafluorophenyl) borate; sulfonium organoboron complexes such as diphenylbenzylsulfonium (n-butyl) triphenylborate; triazine compounds such as 2-methyl-4, 6-bis (trichloromethyl) triazine and 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) triazine.
(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 46]
Figure BDA0003506505710000651
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, R62、R63、R64、R65、R66And R67The remaining radicals in (A) represent, independently of one another, hydrogen or-CH2OR68Radical, R68Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and these phenyl groups and naphthyl groups may further haveSubstituents such as alkyl groups, alkoxy groups, and halogen atoms may be bonded. The number of carbon atoms of the alkyl group and the alkoxy group is 1 to 6. As a group consisting of R68The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.
The melamine-based compounds corresponding to the general formula (6), i.e., the compounds of the following general formula (6-1) include, for example: hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine.
[ chemical formula 47]
Figure BDA0003506505710000652
In the formula (6-1), R62、R63、R64、R65、R66And R67In case one of (a) is an aryl group, R62、R63、R64And R65represents-CH2OR68Radical, R62、R63、R64、R65、R66And R67The remaining groups in (a) represent, independently of each other, a hydrogen atom or-CH2OR68Radical, R68Represents 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 include, for example: tetramethylolbenzoguanamine, tetramethoxymethylbenzguanamine, trimethoxymethylbenzguanamine, tetraethoxymethylbenzguanamine.
Crosslinking agents having methylol or methylol alkyl ether groups may also be used, and examples thereof include: 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 BDA0003506505710000661
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 2 or more kinds may be used in combination. 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, 2-mercaptobenzothiazole
Figure BDA0003506505710000662
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, trihydroxyethyl trimercaptopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), 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, and aliphatic polyfunctional mercapto compounds. These mercapto compounds may be used alone or in combination of 2 or more.
(7) Polymerization inhibitor
The photosensitive colored composition of the present invention may contain a polymerization inhibitor from the viewpoint of shape control of the cured product. It is considered that the inclusion of the polymerization inhibitor inhibits radical polymerization of the lower layer of the coating film, and thereby the taper angle (the angle formed between the support and the cured product in the cross section of the cured product) can be controlled.
Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-cresol (BHT). Of these, 2, 6-di-t-butyl-4-methylphenol is preferable from the viewpoint of shape control. In addition, hydroquinone monomethyl ether and methyl hydroquinone are preferable from the viewpoint of safety to the human body.
The polymerization inhibitor may be used singly or in combination of 2 or more.
In the production of the alkali-soluble resin (b), a polymerization inhibitor may be contained in the resin, and the resin may be used as the polymerization inhibitor of the present invention, or a polymerization inhibitor which may be the same as or different from the polymerization inhibitor in the resin may be added in the production of the photosensitive resin composition.
When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, and is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually 0.3 mass% or less, preferably 0.2 mass% or less, more preferably 0.1 mass% or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 0.0005 to 0.3% by mass, more preferably 0.001 to 0.2% by mass, and still more preferably 0.01 to 0.1% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, the shape control of the cured product tends to be controllable, and when the upper limit value is set to be equal to or lower than the lower limit value, the necessary sensitivity tends to be maintained.
< content ratio of each component in photosensitive coloring composition >
The content of the colorant (a) in the photosensitive coloring composition of the present invention is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more, and is 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, in the total solid content. For example, it is preferably 5 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, yet more preferably 20 to 50% by mass, and particularly preferably 20 to 45% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, light shielding properties tend to be ensured, and when the upper limit value is set to be lower than the lower limit value, patterning properties tend to be improved.
When the photosensitive coloring composition contains an organic coloring pigment, the content thereof is not particularly limited, and is preferably 5% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 5 to 70% by mass, more preferably 20 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the loss of ultraviolet light necessary for curing tends to be suppressed and the light-shielding property tends to be improved, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
(a) When the colorant contains the red pigment and/or the orange pigment, the total content ratio of the red pigment and the orange pigment is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less in the colorant (a). For example, it is preferably 5 to 40% by mass, more preferably 8 to 40% by mass, still more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass. When the lower limit value is not less than the lower limit value, a color tone close to black tends to be formed, and when the upper limit value is not more than the upper limit value, high sensitivity tends to be obtained.
(a) When the colorant contains the blue pigment and/or the violet pigment, the total content ratio of the blue pigment and the violet pigment is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 92% by mass or less, and particularly preferably 90% by mass or less in the colorant (a). For example, it is preferably 30 to 95% by mass, more preferably 50 to 95% by mass, still more preferably 70 to 92% by mass, and particularly preferably 80 to 90% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
When the photosensitive coloring composition contains the black pigment, the content thereof is not particularly limited, and is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 2 to 60% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
When the photosensitive coloring composition contains the organic black pigment, the content thereof is not particularly limited, and the content is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 20% by mass or more, and further preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 2 to 60% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
(a) When the colorant contains an organic black pigment, the content thereof is not particularly limited, and in the colorant (a), the content is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more, and is preferably 100% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. For example, it is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, still more preferably 15 to 80% by mass, and particularly preferably 20 to 70% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
When the photosensitive coloring composition contains carbon black as the inorganic black pigment, the content thereof is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less in the colorant (a). For example, it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 40% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
When the colorant (a) includes the organic coloring pigment and the black pigment, the total content ratio thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and is preferably 100% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less in the colorant (a). For example, it is preferably 5 to 100% by mass, more preferably 10 to 70% by mass, and still more preferably 15 to 50% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the light shielding property tends to be high, and when the upper limit value is not more than the above-mentioned upper limit value, the NMP resistance tends to be good.
(b) The content ratio of the alkali-soluble resin is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 35% by mass or more, and is usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less, of the total solid content of the photosensitive coloring composition of the present invention. For example, it is preferably 5 to 85% by mass, more preferably 5 to 80% by mass, further preferably 10 to 70% by mass, further preferably 20 to 60% by mass, further preferably 30 to 50% by mass, and particularly preferably 35 to 45% by mass. When the lower limit value is set to the value not less than the lower limit value, there is a tendency that the solubility of the unexposed portion in the developer is suppressed from decreasing and the development failure can be suppressed, and when the upper limit value is set to the value not more than the upper limit value, there is a tendency that the solubility of the exposed portion in the developer can be suppressed while maintaining the appropriate sensitivity, and the sharpness and the adhesion of the pattern can be suppressed from decreasing.
(b1) The content of the epoxy (meth) acrylate resin is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less, of the total solid content of the photosensitive coloring composition of the present invention. For example, it is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass. By setting the lower limit value or more, there is a tendency that solubility of an unexposed portion in a developer can be secured, and by setting the upper limit value or less, there is a tendency that dissolution of an exposed portion in a developer can be suppressed while maintaining appropriate sensitivity, and sharpness of a pattern and reduction of adhesiveness can be suppressed.
(b) The content of the (b1) epoxy (meth) acrylate resin contained in the alkali-soluble resin is not particularly limited, and is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more, and is usually 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less. For example, it is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and still more preferably 40 to 80% by mass. By setting the lower limit value or more, there is a tendency that solubility of an unexposed portion in a developer can be secured, and by setting the upper limit value or less, there is a tendency that dissolution of an exposed portion in a developer can be suppressed while maintaining appropriate sensitivity, and sharpness of a pattern and reduction of adhesiveness can be suppressed.
(c) The content of the photopolymerization initiator is not particularly limited, and is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further preferably 3% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less, in the entire solid content of the photosensitive coloring composition of the present invention. For example, it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass, yet more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass. When the lower limit value is set to be equal to or higher than the lower limit value, there is a tendency that sensitivity reduction can be suppressed, and when the upper limit value is set to be equal to or lower than the lower limit value, there is a tendency that solubility reduction in a developing solution of an unexposed portion can be suppressed, and development failure can be suppressed.
When the photopolymerization initiator (c) is used together with a polymerization accelerator, the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, of the total solid content of the photosensitive coloring composition of the present invention. The polymerization accelerator is preferably used in an amount of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, based on 100 parts by mass of the photopolymerization initiator (c). When the content of the polymerization accelerator is not less than the lower limit, there is a tendency that a decrease in sensitivity to exposure light can be suppressed, and when the content is not more than the upper limit, there is a tendency that a decrease in solubility of an unexposed portion in a developer is suppressed, and thus development failure can be suppressed.
When the sensitizing dye is used in addition to the photopolymerization initiator (c), the content thereof is not particularly limited, and is usually 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less of the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity.
(d) The content of the ethylenically unsaturated compound is not particularly limited, and is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% 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, of the total solid content of the photosensitive coloring composition of the present invention. For example, it is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 10 to 15% by mass. When the lower limit value is set to the value higher than the lower limit value, dissolution of the exposed portion in the developer can be suppressed, and sharpness and deterioration of adhesion of the pattern can be suppressed while maintaining appropriate sensitivity.
The content of the total solid content of the photosensitive coloring composition of the present invention is adjusted to be usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less by using the solvent (e). For example, the amount is adjusted to 5 to 50% by mass, preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.
(f) The content of the dispersant is not particularly limited, and is usually 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass. When the lower limit value is not less than the lower limit value, sufficient dispersibility tends to be easily obtained, and when the upper limit value is not more than the upper limit value, the ratio of other components can be relatively kept constant or more, and thus, the decrease in sensitivity, platemaking property, and the like tends to be suppressed.
The content of the dispersant (f1) is not particularly limited, and is usually 1 mass% or more, preferably 3 mass% or more, and more preferably 5 mass% or more, and is usually 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, and more preferably 10 mass% or less, of the total solid content of the photosensitive coloring composition. For example, it is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the voltage holding ratio after ultraviolet irradiation tends to be high.
The content of the dispersant (f1) is not particularly limited, and is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more, and usually 100% by mass or less in the dispersant (f). When the lower limit value is not less than the above-mentioned lower limit value, NMP resistance tends to be good.
The content of the dispersant (f) is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass or less, particularly preferably 30 parts by mass or less, per 100 parts by mass of the colorant (a). For example, it is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 30 parts by mass. When the lower limit value is not less than the above-mentioned lower limit value, sufficient dispersibility tends to be easily obtained, and when the upper limit value is not more than the above-mentioned upper limit value, the proportion of other components is relatively decreased, and thus, the decrease in sensitivity, platemaking property, and the like tends to be suppressed.
On the other hand, the content of the (b) alkali-soluble resin is usually 80 parts by mass or more, preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further preferably 200 parts by mass or more, and particularly preferably 250 parts by mass or more, and usually 700 parts by mass or less, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less, relative to 100 parts by mass of the (d) ethylenically unsaturated compound. For example, it is preferably 80 to 700 parts by mass, more preferably 100 to 700 parts by mass, still more preferably 150 to 500 parts by mass, yet more preferably 200 to 400 parts by mass, and particularly preferably 250 to 300 parts by mass. When the lower limit value is not less than the above-described lower limit value, there is a tendency that an appropriate dissolution development state without peeling or the like is obtained, and when the upper limit value is not more than the above-described upper limit value, there is a tendency that an appropriate dissolution time with respect to the developer can be obtained.
When the adhesion improver is used, the content thereof is not particularly limited, and is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass in the entire solid content of the photosensitive coloring composition. When the lower limit value is set to the value not less than the lower limit value, the effect of improving the adhesion tends to be sufficiently obtained, and when the upper limit value is set to the value not more than the upper limit value, the sensitivity reduction and the formation of defects due to residual after development tend to be suppressed.
When a surfactant is used, the content thereof is not particularly limited, and is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass of the total solid content of the photosensitive coloring composition. When the lower limit value is set to be equal to or higher than the lower limit value, smoothness and uniformity of the coating film tend to be easily exhibited, and when the upper limit value is set to be equal to or lower than the lower limit value, 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 >
The photosensitive coloring composition of the present invention has an Optical Density (OD) per 1 μm film thickness of the coating film of 0.5 or more, preferably 0.7 or more, more preferably 1.0 or more, further preferably 1.3 or more, and particularly preferably 1.5 or more, and is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.0 or less. For example, it is preferably 0.5 to 4.0, more preferably 0.7 to 4.0, further preferably 1.0 to 3.0, further preferably 1.3 to 3.0, and particularly preferably 1.5 to 2.0. When the lower limit value is not less than the above-mentioned lower limit value, sufficient light shielding properties tend to be obtained, and when the upper limit value is not more than the above-mentioned upper limit value, the voltage holding ratio and NMP resistance tend to be good.
The Optical Density (OD) per 1 μm of the coating film may be measured using a coating film obtained by curing the photosensitive coloring composition of the present invention, and may be measured using a coating film obtained by heat curing at 230 ℃ for 20 minutes.
The optical density is a transmission optical density indicating the spectral sensitivity characteristic of the light receiving part by the ISO visual sensitivity in ISO 5-3 standard. Generally, a light source a defined by CIE (international commission on illumination) can be used as the light source. Examples of the measuring instrument that can be used for measuring the transmitted light density include X-Rite 361T (V) of SAKATA INX ENG CO, LTD.
< method for producing photosensitive coloring composition >
The photosensitive coloring composition of the present invention is produced by a usual method.
In general, the colorant (a) is preferably subjected to dispersion treatment in advance using a paint shaker, sand mill, ball mill, roll mill, stone mill, air mill, homogenizer, or the like. By the dispersion treatment, (a) the colorant is micronized, and therefore, the coating characteristics of the resist are improved.
The dispersion treatment is usually preferably performed in a system in which a part or all of (a) the colorant, (e) the solvent, (f) the dispersant, and (b) the alkali-soluble resin are used in combination (hereinafter, the composition obtained in the dispersion treatment may be referred to as "pigment dispersion liquid"). In particular, the use of a polymeric dispersant as the dispersant (f) is preferable because thickening of the obtained pigment dispersion liquid and photosensitive coloring composition over time can be suppressed, that is, dispersion stability is excellent.
Therefore, in the step of producing the photosensitive colored composition, 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 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. In addition, as the content ratio of each colorant in the colorant (a) in the pigment dispersion liquid, those described as the content ratio in the photosensitive coloring composition can be preferably used.
When a liquid containing all the components blended in the colored resin composition is subjected to a dispersion treatment, the highly reactive components may be modified due to heat generation during the dispersion treatment. Therefore, the dispersion treatment is preferably performed in a system containing a polymeric 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 dispersion time may be adjusted as appropriate depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and the appropriate time. The approximate criteria for dispersion are: the gloss of the pigment dispersion liquid is controlled so that the 20-degree specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300. When the gloss of the photosensitive coloring composition is low, many coarse pigment (color material) particles remain due to insufficient dispersion treatment, and there is a possibility that the developability, adhesion, resolution, and the like become insufficient. When the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is broken to generate a large amount of ultrafine particles, and therefore, the dispersion stability tends to be impaired.
The dispersed particle diameter of the pigment dispersed in the pigment dispersion liquid is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method.
Next, the pigment dispersion obtained by the dispersion treatment is mixed with the other components contained in the photosensitive coloring composition to prepare a uniform solution or dispersion. In the production process of the photosensitive coloring composition, fine dust is sometimes mixed into the liquid, and therefore the obtained photosensitive coloring composition is desirably subjected to a filtration treatment by a filter or the like.
[ pigment dispersion for image display device ]
The pigment dispersion liquid for an image display device of the present invention contains (a) a colorant, (e) a solvent, and (f) a dispersant, and particularly, the colorant (a) contains a black pigment, and the dispersant (f) contains a dispersant (f 1).
As the colorant (a), the solvent (e), and the dispersant (f) in the pigment dispersion liquid for an image display device of the present invention, those listed as the same items in the photosensitive coloring composition of the present invention can be preferably used. Similarly, as the black pigment and the dispersant (f1) in the pigment dispersion liquid for an image display device of the present invention, those listed as the same items in the photosensitive coloring composition of the present invention can be preferably used.
The content of the colorant (a) in the pigment dispersion for an image display device of the present invention is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less in the entire solid content. For example, it is preferably 30 to 80% by mass, more preferably 50 to 75% by mass, and still more preferably 60 to 70% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the voltage holding ratio and NMP resistance after ultraviolet irradiation tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the dispersibility tends to be good.
In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the black pigment is not particularly limited, and is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less in the entire solid content. For example, it is preferably 30 to 80% by mass, more preferably 50 to 75% by mass, and still more preferably 60 to 70% by mass. When the lower limit value is not less than the above-mentioned lower limit value, the voltage holding ratio and NMP resistance after ultraviolet irradiation tend to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the dispersibility tends to be good.
In the pigment dispersion liquid for an image display device of the present invention, it is desirable that the black pigment contains an organic black pigment represented by the aforementioned structural formula (1) from the viewpoint of light-shielding properties when used as a photosensitive coloring composition.
The content of the organic black pigment of the formula (1) with respect to the colorant (a) is preferably 10% by mass or more, more preferably 40% by mass or more, further preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 98% by mass or more in the entire colorant (a).
In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the (f) dispersant is not particularly limited, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and particularly preferably 10% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less in the entire solid content. For example, it is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 20% by mass, and particularly preferably 10 to 15% by mass. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, voltage holding ratio and NMP resistance after ultraviolet irradiation tend to be good.
In the pigment dispersion liquid for an image display device of the present invention, the content ratio of the dispersant (f1) is not particularly limited, and is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more, and is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less in the entire solid content. For example, it is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, still more preferably 8 to 20% by mass, and particularly preferably 10 to 15% by mass. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, voltage holding ratio and NMP resistance after ultraviolet irradiation tend to be good.
The content of the dispersant (f1) is not particularly limited, and is usually 10% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more, and usually 100% by mass or less in the dispersant (f). When the lower limit value is not less than the above-mentioned lower limit value, NMP resistance tends to be good.
The pigment dispersion liquid for an image display device of the present invention is prepared by using the solvent (e) so that the content of the total solid content is adjusted to be usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less. Preferably, the amount is adjusted to 10 to 40% by mass, more preferably 15 to 35% by mass, and still more preferably 20 to 30% by mass.
[ cured product ]
The cured product of the present invention can be obtained by curing the photosensitive colored composition of the present invention. The cured product of the present invention can be preferably used as a colored spacer.
In addition, the photosensitive coloring composition of the invention cured product can be preferably used as the partition wall.
[ colored spacer ]
Next, a colored spacer using the photosensitive colored composition of the present invention will be described according to a method for producing the same.
(1) Support body
The material of the support for forming the colored spacer is not particularly limited as long as it has an appropriate strength. The transparent substrate is mainly used, and examples of the material thereof include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, and various glasses. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the 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, for example, corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent and a urethane resin, if 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 in the same applications as those of known photosensitive coloring compositions for color filters, and hereinafter, a specific example of a method for forming a black spacer using the photosensitive coloring composition of the present invention will be described with respect to a case where the composition is used as a color spacer (black spacer).
Generally, a photosensitive coloring composition is supplied in a film or pattern form by a method such as coating on a substrate on which a black photo spacer is to be provided, and a solvent is dried. Next, a pattern is formed by a method such as photolithography in which exposure and development are performed. Then, additional exposure and thermal curing are performed as necessary, thereby forming a black photo spacer on the substrate.
(3) Formation of colored spacers
[1] Method for supplying substrate
The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. The supply method may be performed by a conventionally known method, for example, spin coating, Wire bar (Wire bar) method, flow coating, die coating, roll coating, or spray coating. The ink may be supplied in a pattern by, for example, an ink jet method or a printing method. Among these, the use amount of the coating liquid can be greatly reduced by the die coating method, and the foreign matter generation can be suppressed without being affected by fogging or the like attached when the spin coating method is used.
The amount of coating varies depending on the application, and for example, in the case of a black spacer, the coating is usually applied in a dry film thickness of 0.5 to 10 μm, preferably 1 to 9 μm, and particularly preferably 1 to 7 μm. 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 small, the occurrence of a streak defect in the liquid crystal panel can be suppressed.
When the black spacers having different heights are formed at one time by photolithography using the photosensitive colored composition of the present invention, the black spacers to be finally formed have different heights.
As the substrate, a known substrate such as a glass substrate can be used. The substrate surface is preferably planar.
[2] Drying method
The drying after the supply of the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. A combination of a reduced-pressure drying method of drying in a reduced-pressure chamber without increasing the temperature may be used.
The drying conditions may be 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 ℃ and 15 to 5 minutes, preferably 50 to 110 ℃ and 30 to 3 minutes, depending on the kind of solvent component and the performance of the dryer to be used.
[3] Exposure method
The exposure is performed by a light source that superimposes a negative mask pattern on a coating film of the photosensitive coloring composition and irradiates ultraviolet rays or visible rays through the mask pattern. When exposure is performed using an exposure mask, a method of bringing the exposure mask close to a coating film of the photosensitive coloring composition; a method of disposing an exposure mask at a position distant from a coating film of the photosensitive coloring composition and projecting exposure light through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be employed. If necessary, 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, 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) which is an opening having a smaller average light transmittance than the highest average light transmittance (full transmission opening) as a plurality of openings is used. 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 using a film of, for example, a chromium-based, molybdenum-based, tungsten-based, or silicon-based material as an absorber is known.
The light source used for the exposure is not particularly limited. Examples of the light source include: lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, and near-infrared semiconductor laser. When light of a specific wavelength is irradiated and used, an optical filter may be used.
The optical filter may be of a type that can control the light transmittance of the exposure wavelength with a thin film, for example, and the material used in this case may be, for example: cr compounds (Cr oxide, nitride, oxynitride, fluoride, etc.), MoSi, Si, W, 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. The aqueous solution of the basic compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or 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: isopropanol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol. These organic solvents may be used in combination of 2 or more. The organic solvent may be used alone, or may be used in combination with water or an aqueous solution of a basic compound.
The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 to 50 ℃, preferably 15 to 45 ℃, and more preferably 20 to 40 ℃. The developing method may be, for example, a dip developing method, a spray developing method, a brush developing method, or an ultrasonic developing method.
[5] Additional exposure and thermal curing treatment
The substrate after development may be additionally exposed by the same method as the above exposure method, or may be subjected to a heat curing treatment, if necessary. The heat curing treatment conditions were as follows: the temperature is 100-280 ℃, preferably 150-250 ℃ and the time is 5-60 minutes.
The size, shape, etc. of the colored spacer of the present invention can be appropriately adjusted according to the specification of a color filter using the colored spacer, and the photosensitive colored composition of the present invention is particularly useful for simultaneously forming black photo spacers having different heights, such as a spacer and an auxiliary spacer, by a photolithography method. The height of the spacer is usually about 2 to 7 μm, and the height of the auxiliary spacer is usually about 0.2 to 1.5 μm lower than that of the spacer.
In addition, from the viewpoint of light-shielding properties, the colored spacer of the present invention has an Optical Density (OD) per 1 μm of preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and particularly preferably 1.8 or more, and is usually 4.0 or less, preferably 3.0 or less. For example, it is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. The Optical Density (OD) is a value measured by a method described later.
[ partition walls ]
The photosensitive colored composition of the present invention can be preferably used for forming partition walls, particularly partition walls for partitioning organic layers of an organic electroluminescent device. Examples of the organic layer used in the organic electroluminescent element include an organic layer used in a hole injection layer, a hole transport layer, and a hole transport layer over a hole injection layer as described in japanese patent laid-open publication No. 2016-165396.
The partition wall using the photosensitive coloring composition of the present invention will be described according to the method for producing the same.
(1) Support body
As the support and the substrate for forming the partition walls, the same ones as those for forming the colored spacers described above can be used.
(2) Partition wall
Hereinafter, the case of using the photosensitive coloring composition as a partition wall will be described according to a specific example of a method for forming a partition wall using the photosensitive coloring composition of the present invention.
Generally, a photosensitive coloring composition is supplied in a film or pattern form by a method such as coating on a substrate on which partition walls are to be formed, 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 thermosetting treatment are performed as necessary, thereby forming partition walls on the substrate.
(3) Formation of spacer
In the method of forming the partition wall using the photosensitive coloring composition of the present invention, the method of supplying the photosensitive coloring composition to the substrate, the drying method, the exposure method, the developing method, and the specific methods of the additional exposure and the thermosetting treatment may be the same methods as those for forming the above-described colored spacer.
The size, shape and the like of the partition wall of the present invention can be suitably adjusted according to the specification and the like of the organic electroluminescent element using the partition wall, and the height of the partition wall formed by the photosensitive coloring composition of the present invention is usually about 0.5 to 10 μm.
From the viewpoint of light-shielding properties, the Optical Density (OD) per 1 μm of the partition wall of the present invention is preferably 0.7 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. For example, it is preferably 0.7 to 4.0, more preferably 1.2 to 4.0, further preferably 1.5 to 3.0, and particularly preferably 1.8 to 3.0. The Optical Density (OD) is a value measured by a method described later.
[ organic electroluminescent element ]
The organic electroluminescent element of the present invention comprises a cured product, for example, a partition wall, formed from the photosensitive colored composition.
For example, various organic electroluminescent elements can be manufactured using the substrate having the partition wall pattern manufactured by the above-described method. The method of forming the organic electroluminescent element is not particularly limited, but the organic electroluminescent element is preferably produced by forming a pattern of partition walls on a substrate by the above-mentioned method and then forming an organic layer such as a pixel by a wet process such as vapor deposition, casting, spin coating, or ink jet printing, in which a functional material is sublimated in a vacuum state and deposited in a region surrounded by the partition walls on the substrate to form a film.
Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall.
The light-emitting layer may be an organic electroluminescent layer as described in japanese patent laid-open nos. 2009-146691 and 5734681. In addition, quantum dots as described in japanese patent No. 5653387 and japanese patent No. 5653101 may be used.
The layer structure is not limited to this, and for example, each of the hole transport layer and the electron transport layer may have a laminated structure of two or more layers from the viewpoint of light emission efficiency. The thickness of each layer is not particularly limited, and is usually 1 to 500nm from the viewpoint of light emission efficiency and luminance.
The organic electroluminescent element may be formed by dividing each of RGB colors into each of the openings, or two or more colors may be stacked in 1 opening. From the viewpoint of improving reliability, the organic electroluminescent element may be provided with a sealing layer. The sealing layer has a function of preventing a decrease in light emission efficiency by adsorbing moisture in the air to the organic electroluminescent element. From the viewpoint of improving light extraction efficiency, the organic electroluminescent element may have a low reflection film at the interface with air. By disposing the low reflection film at the interface between the air and the element, the gap in refractive index can be reduced, and suppression of reflection at the interface can be expected. For such a low reflection film, a technique such as a moth-eye structure or an ultra-multilayer film can be applied.
When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light from a light-emitting layer of some pixels from leaking to other pixels, and when an electrode or the like is made of a metal, it is necessary to prevent deterioration of image quality due to reflection of external light.
In the organic electroluminescent element, electrodes need to be provided on the upper and lower surfaces of the partition walls, and therefore, from the viewpoint of insulation, the partition walls are preferably high in resistance and low in dielectric constant. Therefore, in order to impart light-shielding properties to the partition walls, when a colorant is used, the organic pigment having high electric resistance and low dielectric constant is preferably used.
[ image display apparatus ]
The image display device of the present invention comprises the cured product of the present invention.
For example, an image display device such as a liquid crystal display device including the cured product of the present invention can be manufactured by forming an alignment film on a liquid crystal driving substrate (array substrate) having a color spacer formed from the photosensitive color composition of the present invention, bonding the alignment film to a counter electrode substrate to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell.
In addition, the counter electrode substrate side is provided with the photosensitive coloring composition of the invention formed by the colored spacer, and with the liquid crystal driving substrate (array substrate) laminated to form a liquid crystal cell, in the liquid crystal cell formed by injection of liquid crystal, thereby manufacturing the invention containing cured material of liquid crystal display device and other image display devices.
As described in jp 2014-215614 a, the liquid crystal alignment property can be improved by injecting liquid crystal into a liquid crystal cell using a specific alignment substance and then irradiating the liquid crystal cell with ultraviolet light.
The image display device of the present invention may be an organic EL display device including organic electroluminescent elements and partition walls made of a cured product of the present invention.
The organic EL display device is not particularly limited in type and structure as long as it includes the above-described organic electroluminescent element, and for example, can be assembled by a conventional method using an active-drive type organic electroluminescent element. For example, the organic EL display can be formed by a method described in "organic EL display" (OHM corporation, 16 years, 8 months, 20 days, wainsch, andkyush, hamtian english-fortune). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.
[ Lighting ]
The organic electroluminescent element comprising the cured product of the present invention can be used for illumination. The type and structure of the illumination are not particularly limited, and the organic electroluminescent element comprising the cured product of the present invention can be assembled by a conventional method. The organic electroluminescent element may be of a simple matrix driving type or an active matrix driving type.
In order to make the illumination emit white light, an organic electroluminescent element that emits white light may be used. Further, the color mixing function may be provided by combining organic electroluminescent elements having different emission colors so that the color mixture of the respective colors becomes white, or by adjusting the ratio of the color mixture.
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 constituent components of the pigment dispersion and the photosensitive coloring composition used in the following examples and comparative examples, and the methods for evaluating them, are as follows.
< alkali soluble resin-I >
145 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was stirred while being replaced with nitrogen, and the temperature was raised to 120 ℃. To this solution, 66 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., Ltd.) were added dropwise, then 8.47 parts by mass of 2, 2' -azobis-2-methylbutyronitrile was added dropwise over 3 hours, and further stirring was continued at 90 ℃ for 2 hours. Subsequently, the inside of the reaction vessel was replaced with air, and 43.2 parts by mass of acrylic acid were charged with 0.7 part by mass of tris (dimethylaminomethyl) phenol and 0.12 part by mass of hydroquinone, and the reaction was continued at 100 ℃ for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 part by mass of triethylamine were added thereto, and the mixture was reacted at 100 ℃ for 3.5 hours. The obtained alkali-soluble resin I had a weight-average molecular weight Mw of 8400 and an acid value of 80mgKOH/g as measured by GPC.
< alkali soluble resin-II >
"XD 1000" (polydiglycidyl ether of dicyclopentadiene-phenol polymer, epoxy equivalent 252) produced by Kakkiso K.K. 300 parts by mass, acrylic acid 87 parts by mass, p-methoxyphenol 0.2 part by mass, triphenylphosphine 5 parts by mass, and propylene glycol monomethyl ether acetate 255 parts by mass were charged in a reaction vessel, and stirred at 100 ℃ until the acid value reached 3.0 mgKOH/g. Subsequently, 145 parts by mass of tetrahydrophthalic anhydride was further added, and the reaction was carried out at 120 ℃ for 4 hours. The alkali-soluble resin II thus obtained had a weight-average molecular weight Mw of 2600 and an acid value of 106mgKOH/g, as measured by GPC.
< pigment-I >
C.i. pigment blue 60
< pigment-II >
C.i. pigment orange 64
< pigment-III >
C.i. pigment violet 29
< pigment-IV >
Irgaphor (registered trademark) Black S0100 CF (having a chemical structure represented by the following formula (I-1))
[ chemical formula 48]
Figure BDA0003506505710000841
< dispersant-I >
A methacrylic A-B-A triblock copolymer comprising an A block comprising a repeating unit having a solventborne group and a B block comprising a repeating unit having a pigment-adsorbing group, which has repeating units represented by the following formulae (a) to (g), and which has an amine value of 48mgKOH/g and a theoretical molecular weight of 8,300.
The content ratios of the repeating units represented by the following formulae (a) to (g) in all the repeating units are respectively: (a)40.4 mol% (26.6 mass%), (b)13.7 mol% (12.8 mass%), (c)9.3 mol% (12.1 mass%), (d)7.7 mol% (8.9 mass%), (e)2.7 mol% (4.9 mass%), (f)17.0 mol% (17.6 mass%), and (g)9.2 mol% (17.1 mass%).
[ chemical formula 49]
A block
Figure BDA0003506505710000851
[ chemical formula 50]
B block
Figure BDA0003506505710000852
< dispersant-II >
"BYK-LPN 6919" manufactured by BYK-Chemie, Inc., which is a methacrylic A-B block copolymer comprising an A block comprising a repeating unit having a solvent-philic group and a B block comprising a repeating unit having a pigment adsorbing group, has repeating units of the following formulae (2a) and (3a), and has an amine value of 120mgKOH/g and an acid value of 1mgKOH/g or less.
The content ratio of the repeating unit represented by the following formula (2a) and the repeating unit represented by the following formula (3a) in all the repeating units was 33.3 mol% and 6.7 mol%, respectively.
[ chemical formula 51]
Figure BDA0003506505710000861
< dispersant-III >
2.92 parts by mass of dispersant-II (solid content, PGMEA solution) and 0.35 part by mass of phenylphosphonic acid were mixed, and the solid content of the stirred mixture was used as dispersant-III.
The dispersant-III is assumed to have the following repeating units of the formulae (1a-1), (2a) and (3 a). The content ratios of the repeating unit represented by the following formula (1a-1), the repeating unit represented by the following formula (2a), and the repeating unit represented by the following formula (3a) in all the repeating units were 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.
[ chemical formula 52]
Figure BDA0003506505710000862
< dispersant-IV >
2.88 parts by mass of dispersant-II (amount of solid component, PGMEA solution) and 0.38 part by mass of benzenesulfonic acid monohydrate were mixed, and the solid component of the stirred mixture was used as dispersant-IV.
The dispersant-IV is assumed to have repeating units represented by the following formulas (1a-2), (2a) and (3 a). The content ratios of the repeating unit represented by the following formula (1a-2), the repeating unit represented by the following formula (2a), and the repeating unit represented by the following formula (3a) in all the repeating units were 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.
[ chemical formula 53]
Figure BDA0003506505710000871
< dispersant-V >
2.85 parts by mass of dispersant-II (amount of solid component, PGMEA solution) and 0.41 part by mass of p-toluenesulfonic acid were mixed, and the solid component of the stirred mixture was used as dispersant-V.
The dispersant-V is assumed to have repeating units represented by the following formulas (1a-3), (2a) and (3 a). The content ratios of the repeating unit represented by the following formula (1a-3), the repeating unit represented by the following formula (2a), and the repeating unit represented by the following formula (3a) in all the repeating units were 13.0 mol%, 20.3 mol%, and 6.7 mol%, respectively.
[ chemical formula 54]
Figure BDA0003506505710000872
< dispersant-VI >
A methacrylic A-B diblock copolymer comprising an A block comprising a repeating unit having a solvent-philic group and a B block comprising a repeating unit having a pigment-adsorbing group, having repeating units of the following formulae (h) to (n), and having an amine value of 70 mgKOH/g.
The content ratios of the repeating units represented by the following formulae (h) to (n) in all the repeating units are respectively: (h)33.3 mol%, (i)13.3 mol%, (j)6.7 mol%, (k)6.7 mol%, (l)6.7 mol%, (m)22.2 mol%, and (n)11.1 mol%.
[ chemical formula 55]
A block
Figure BDA0003506505710000881
[ chemical formula 56]
B block
Figure BDA0003506505710000882
< dispersant-VII >
2.90 parts by mass of dispersant-II (amount of solid component, PGMEA solution) and 0.37 part by mass of methyl p-toluenesulfonate were mixed, and the solid component of the stirred mixture was used as dispersant-VII.
dispersant-VII is assumed to have repeating units of the following formulae (1a-5), (2a), and (3 a). The content ratios of the repeating unit represented by the following formula (1a-4), the repeating unit represented by the following formula (2a), and the repeating unit represented by the following formula (3a) in all the repeating units were 11.7 mol%, 21.6 mol%, and 6.7 mol%, respectively.
[ chemical formula 57]
Figure BDA0003506505710000883
< solvent-I >
PGMEA: propylene glycol monomethyl ether acetate
< solvent-II >
MB: 3-methoxy-1-butanol
< photopolymerization initiator-I >
Oxime ester photopolymerization initiator having the following chemical structure
[ chemical formula 58]
Figure BDA0003506505710000891
< photopolymerization initiator-II >
Oxime ester photopolymerization initiator having the following chemical structure
(4-Acetoxyimino-5- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -5-oxopentanoic acid methyl ester)
[ chemical formula 59]
Figure BDA0003506505710000892
< ethylenically unsaturated Compound >
DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kabushiki Kaisha
< surfactant >
Megafac F-559 manufactured by DIC Ltd
< additive >
KAYAMER PM-21 (methacryloyl group-containing phosphate ester) manufactured by Nippon Kabushiki Kaisha
< evaluation of viscosity >
The viscosity of the pigment dispersion liquid thus prepared was measured with a RE-85L viscometer (measurement conditions: 23 ℃ C., 20rpm) manufactured by Toyobo industries Co., Ltd.
< measurement of optical Density per Unit film thickness (Unit OD value) >
The optical density per unit film thickness was measured in the following order.
First, the photosensitive coloring composition obtained was applied onto a glass substrate using a spin coater so that the film thickness after heat curing was 3.0 μm, dried under reduced pressure for 1 minute, and then dried at 90 ℃ for 140 seconds using a hot plate. The obtained coating film was exposed to light without using an exposure mask. As an irradiation light source, an intensity of 45mW/cm at a wavelength of 365nm was used2High pressure mercury lamp and exposureSet to 50mJ/cm2. Subsequently, the substrate was heated and cured in an oven at 230 ℃ for 20 minutes, whereby a resist-coated substrate 1 was obtained.
The optical density (OD value) of the resulting resist-coated substrate 1 was measured using a transmission type densitometer (color temperature of an illumination light source: about 2850K (corresponding to CIE standard light source A), spectral sensitivity characteristics of a light receiving part: ISO visual sensitivity under ISO 5-3 standard) manufactured by X-Rite, Inc., and the film thickness was measured using a non-contact surface/layer cross-sectional shape measuring system VertScan (R)2.0 manufactured by Traji corporation, and the optical density (unit OD value) per unit film thickness (1 μm) was calculated from the optical density (OD value) and the film thickness. The OD value is a numerical value indicating light-shielding ability, and a larger numerical value indicates higher light-shielding ability.
< evaluation of Voltage Holding Ratio (VHR) and ion Density >
Each photosensitive coloring composition was applied to an electrode substrate having an ITO film formed on one surface thereof, vacuum-dried for 1 minute, and then dried on a hot plate at 90 ℃ for 140 seconds. The obtained coating film was irradiated with a high pressure mercury lamp at 50mJ/cm2Illuminance of 45mW/cm2The image exposure is performed under the exposure conditions of (1). Subsequently, the development was carried out by spraying with a water pressure of 0.15MPa at 25 ℃ using an aqueous solution of potassium hydroxide of about 0.05 mass% at 25 ℃, and then the development was terminated with pure water and rinsed with a water-washing spray. The shower development time is adjusted to 10 to 20 seconds and is set to about 1.6 times the time (interruption time) for dissolving and removing the unexposed photosensitive coloring composition layer. Subsequently, the resultant was cured by heating in an oven at 230 ℃ for 20 minutes, thereby obtaining an electrode substrate for evaluation.
In addition, an empty cell was produced according to the method described in international publication No. 2018/151079.
The obtained empty cell was filled with a liquid crystal (MLC-6608 manufactured by Merck Japan) and the peripheral portion was sealed with a UV curable sealant. The liquid crystal cell was annealed (heated at 105 ℃ for 2.5 hours in a hot air circulating furnace), and the liquid crystal cell for measurement was completed.
The voltage was applied to the prepared liquid crystal cell for measurement under the conditions of a voltage of 5V, 0.6Hz, and a frame time of 1667msec, and the voltage holding ratio before ultraviolet irradiation was measured by "liquid crystal property evaluation device model-6254" manufactured by TOYO Corporation. The voltage holding ratio is an index of electrical reliability. The higher the voltage holding ratio, the more preferable.
Then, a triangular wave having a frequency of 0.1Hz and ± 3V was applied to the liquid crystal cell for measurement using the same apparatus, and the current at that time was measured, and a waveform of the temporal change in current was obtained. The area of the impurity ion peak in the waveform was measured, and the ion density (pC) before ultraviolet irradiation was measured.
Then, using a high pressure mercury lamp at 18J/cm2Illuminance of 40mW/cm2The liquid crystal cell for measurement was irradiated with ultraviolet rays. The voltage holding ratio after the ultraviolet irradiation and the ion density after the ultraviolet irradiation were measured using the liquid crystal cell for measurement after the ultraviolet irradiation in the same manner as described above.
< evaluation of NMP resistance >
Evaluation of N-methylpyrrolidone (NMP) resistance was carried out in the following order.
First, the obtained photosensitive coloring composition was applied to an IZO substrate using a spin coater so that the film thickness after heat curing was 3.0 μm, dried under reduced pressure for 1 minute, and then dried at 90 ℃ for 140 seconds using a hot plate. The obtained coating film was exposed to light without using an exposure mask. As an irradiation light source, an intensity of 45mW/cm at a wavelength of 365nm was used2The exposure amount of the high-pressure mercury lamp is 50mJ/cm2. Next, a developer solution containing an aqueous solution of 0.05 mass% of potassium hydroxide and 0.08 mass% of a nonionic surfactant (a-60, manufactured by kao corporation) was used, and shower development was performed at 25 ℃ under a water pressure of 0.05MPa, and then the development was terminated with pure water, and washing was performed by water spray. The time for which the unexposed coating film was dissolved and removed was measured in advance, and the shower development time was set to 1.6 times the time. Then, heat-cured in an oven at a temperature of 230 ℃ for 20 minutes, to obtain a resist-coated substrate 2.2 measurement substrates (2.5 cm. times.1.0 cm) were cut out from the resulting resist-coated substrate 2, and immersed in the solutionA10 mL ampoule containing 8mL of NMP was used. Then, the ampoule bottle containing the substrate for measurement was left to stand in a hot bath at 80 ℃ for 40 minutes to perform an NMP elution test. After leaving the flask for 40 minutes, the ampoule was taken out from the hot bath, and the absorbance of the NMP-dissolved solution was measured at 1nm intervals in a wavelength range of 300 to 800nm by a spectrophotometer (UV-3100 PC, Shimadzu corporation). A halogen lamp and a deuterium lamp (switching wavelength: 360nm) were used as a light source, a photomultiplier tube was used as a detector, and the slit width was 2nm under the measurement conditions. Further, the sample solution (NMP-eluted solution) was placed in a1 cm-square quartz cell and measured. The absorbance is a dimensionless quantity indicating how much the light intensity shows attenuation when passing through a certain object in the spectroscopic method, and is defined by the following equation.
A (absorbance) — log10(I/I0) (I: intensity of transmitted light, I0: incident light intensity)
Further, the light intensity of the light incident on the sample solution and the NMP solution alone from the same light source can be regarded as I0And the intensity of light transmitted through the sample solution is regarded as I. Thus, in the above formula (I/I)0) The transmittance is shown, and the absorbance a is a value obtained by logarithmically expressing the reciprocal of the transmittance. The absorbance a is a marker used for calculating the concentration or the like of a substance contained in a sample solution. When the absorbance a is 0, the state where light is not absorbed at all (transmittance 100%) is shown, and when the absorbance a is infinity, the state where light is not transmitted at all (transmittance 0%) is shown. That is, the higher the absorbance, the more the resist coating composition eluted to NMP, and the worse the NMP resistance. The spectral area of the absorbance was calculated, and NMP resistance was evaluated according to the following criteria. The spectral area of absorbance as the evaluation criterion may be represented by the sum of absorbances at respective wavelengths, and is represented by the sum of eluted resist components.
Evaluation criteria for NMP resistance: determination based on the spectral area value of absorbance (wavelength 300 to 800nm)
A: less than 100
B: over 100 and 200 or less
C: over 200
< preparation of pigment Dispersion 1 to 7 >
The pigment, the dispersant, the alkali-soluble resin, and the solvent described in table 1 were mixed in the mass ratio described in table 1. The mixed solution was subjected to a dispersion treatment for 3 hours at a temperature of 25 to 45 ℃ by 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 to 7 were prepared.
The amount of the solvent in table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin. The evaluation results of the viscosity of the pigment dispersion measured by the above-described method are shown in table 1.
Figure BDA0003506505710000931
Examples 1 to 4 and comparative examples 1 to 6
Photosensitive coloring compositions of examples 1 to 4 and comparative examples 1 to 6 were prepared by adding each component so that the content ratio of the solid content of each component in the total solid content became the value shown in table 2, further adding PGMEA so that the content ratio of the total solid content was 22 mass%, and stirring and dissolving the components. Table 2 shows the evaluation results of the unit OD value, the Voltage Holding Ratio (VHR), the ion density, and the NMP resistance measured by the above-described methods.
Figure BDA0003506505710000951
As is clear from table 2, in the photosensitive coloring composition of comparative example 4, the counter ion in the repeating unit represented by the formula (1) in the dispersant-VI is not a counter anion represented by the formula (2) but a halogen ion, and thus the voltage holding ratio, the ion density, and the NMP resistance after ultraviolet irradiation are significantly poor. On the other hand, in the photosensitive coloring composition of comparative example 5, the optical density per unit film thickness was less than 0.5, and the composition was satisfactory even without the dispersant described in the present application, and the problem of the present application did not occur. This is presumed to be because the pigment in comparative example 5 had a small amount of impurities, a small amount of free counter anions of the dispersant, and the like.
The photosensitive coloring composition of comparative example 1 was significantly inferior in NMP resistance. This is presumed to be because the dispersant-III contained in the photosensitive coloring composition of comparative example 1 forms a salt with a counter anion of an ammonium group as a phosphonic acid ion derived from a weak acid, but is derived from a weak acid and is easily converted back to a phosphonic acid and an amino group, and when the composition is immersed in an amine-based solvent such as NMP, the compatibility of the dispersant is high, the dispersant is easily released from the coloring agent, the amount of the dispersant adsorbed and coated on the surface of the coloring agent decreases, and a part of the coloring agent is eluted as impurities.
On the other hand, the photosensitive coloring compositions of comparative examples 2 and 3 both had a low voltage holding ratio before ultraviolet irradiation and a low voltage holding ratio after ultraviolet irradiation. This is presumed to be because the counter anions of the ammonium groups of the dispersants-IV and V contained in the photosensitive coloring compositions of comparative examples 2 and 3, i.e., the toluene sulfonic acid anion and the benzene sulfonic acid anion, are stable anions derived from a strong acid, and the remaining dispersant sulfonic acid anions not adsorbed to the pigment are dissolved in the liquid crystal to lower the voltage holding ratio, and the counter anions released by the ultraviolet irradiation further increase to further lower the voltage holding ratio.
In addition, the photosensitive colored composition of comparative example 6 had a low voltage holding ratio before ultraviolet irradiation and a low voltage holding ratio after ultraviolet irradiation. This is presumed to be because methyl tosylate contained in the dispersant-VI contained in the photosensitive colorant of comparative example 6 is easily released, and further released by ultraviolet irradiation and dissolved in the liquid crystal to lower the voltage holding ratio.
On the other hand, the photosensitive coloring composition of example 1 had good NMP resistance, and the voltage holding ratio before ultraviolet irradiation and the voltage holding ratio after ultraviolet irradiation were both good
This is presumed to be because the counter anion represented by the general formula (2) of the dispersant-I contained in the photosensitive colored composition of example 1 is derived from an ester, not an acid-derived anion, and the ammonium group is not converted back to an amino group, and NMP resistance is good.
Further, since the counter anion is stably bonded to the ammonium group in the form of an anion derived from an ester, even when an excessive dispersant remains in the cured product, the counter anion is not easily released in the liquid crystal as an anion, and hardly affects the alignment property of the liquid crystal, and the voltage holding ratio is good both before and after the ultraviolet irradiation.
As in the photosensitive colored composition of example 3, the lower the unit OD, the better the voltage holding ratio and NMP resistance. This is presumably because the elution of impurities from the pigment is small. In addition, as in the photosensitive colored compositions of examples 2 and 4, even when the organic black pigment of the structural formula (1) is contained, the voltage holding ratio and NMP resistance are good.

Claims (12)

1. A photosensitive coloring composition, 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,
the optical density of the coating film per 1 [ mu ] m film thickness after the photosensitive coloring composition is cured is more than 0.5,
the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1),
Figure FDA0003506505700000011
in the formula (1), R1～R3Each independently is an optionally substituted alkyl group or an optionally substituted aryl group, optionally R1～R32 or more of them are bonded to each other to form a ring structure,
R4is a hydrogen atom or a methyl group,
x is a linking group having a valence of 2,
Y-is a counter anion represented by the following general formula (2),
Figure FDA0003506505700000012
in the formula (2), R5Is an alkyl group optionally having a substituent.
2. The photosensitive coloring composition according to claim 1, wherein the colorant (a) comprises 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.
3. The photosensitive coloring composition according to claim 1 or 2, wherein the (a) colorant comprises a black pigment.
4. The photosensitive coloring composition according to claim 3, wherein the black pigment comprises an organic black pigment.
5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein a content ratio of the colorant (a) is 10% by mass or more in the entire solid content.
6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the amine value of the dispersant (f1) is 30mgKOH/g or more.
7. The photosensitive coloring composition according to any one of claims 1 to 6, which is used for forming a coloring spacer.
8. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7.
9. An image display device comprising the cured product according to claim 8.
10. A pigment dispersion liquid for an image display device, comprising: (a) a colorant, (e) a solvent, and (f) a dispersant, wherein,
the (a) colorant contains a black pigment,
the dispersant (f) contains a dispersant (f1) having a repeating unit represented by the following general formula (1),
Figure FDA0003506505700000021
in the formula (1), R1～R3Each independently is an optionally substituted alkyl group or an optionally substituted aryl group, optionally R1～R32 or more of them are bonded to each other to form a ring structure,
R4is a hydrogen atom or a methyl group,
x is a linking group having a valence of 2,
Y-is a counter anion represented by the following general formula (2),
Figure FDA0003506505700000022
in the formula (2), R5Is an alkyl group optionally having a substituent.
11. The pigment dispersion liquid for an image display device according to claim 10, wherein the black pigment comprises an organic black pigment.
12. The pigment dispersion liquid for an image display device according to claim 10 or 11, wherein an amine value of said dispersant (f1) is 30mgKOH/g or more.
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