CN115629522A - Photosensitive resin composition, photosensitive resin layer using same, color filter, and electronic device - Google Patents

Photosensitive resin composition, photosensitive resin layer using same, color filter, and electronic device Download PDF

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CN115629522A
CN115629522A CN202210755246.4A CN202210755246A CN115629522A CN 115629522 A CN115629522 A CN 115629522A CN 202210755246 A CN202210755246 A CN 202210755246A CN 115629522 A CN115629522 A CN 115629522A
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chemical formula
photosensitive resin
resin composition
substituted
represented
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郑周昊
金善大
辛明晔
李珍雅
张春根
郑义树
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/02—Coumarine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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Abstract

The invention provides a photosensitive resin composition, a photosensitive resin layer manufactured by using the same, a color filter comprising the photosensitive resin layer and an electronic device comprising the color filter. The photosensitive resin composition includes a colorant, wherein the colorant includes a dye represented by chemical formula 1, a core-shell structure dye, and a phthalocyanine-based dye. (in chemical formula 1, each substituent is as defined in the specification) [ chemical formula 1]]
Figure DDA0003722255830000011

Description

Photosensitive resin composition, photosensitive resin layer using same, color filter, and electronic device
Cross Reference to Related Applications
This application claims priority and benefit of korean patent application No. 10-2021-0087302, filed on korean intellectual property office at 7/2/2021, the entire contents of which are incorporated herein by reference.
Technical Field
The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the same, a color filter including the photosensitive resin layer, and an electronic device including the color filter.
Background
Among many types of displays, liquid crystal display devices have advantages of brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely used for laptop computers, monitors, and TV screens. The liquid crystal display device includes: a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed; and an upper substrate on which an active circuit portion including a liquid crystal layer, a thin film transistor, and a capacitor layer, and an ITO pixel electrode are formed. The color filter is formed in the pixel region by sequentially stacking a plurality of color filters (generally, formed of a plurality of colors, typically three primary colors of red (R), green (G), and blue (B)) in a predetermined order to form each pixel, and a black matrix layer is placed in a predetermined pattern on a transparent substrate to form a boundary between the pixels.
The pigment dispersion method, one of the methods of forming a color filter, provides a color thin film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix, exposing the formed pattern to light, removing the unexposed portion with a solvent, and thermally curing it. A color photosensitive resin composition for manufacturing a color filter according to a pigment dispersion method generally includes an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives. The pigment dispersion method is actively applied to manufacture LCDs for mobile phones, laptop computers, monitors, and TVs. However, recently, improved performance and excellent pattern characteristics have been required for photosensitive resin compositions for color filters used in pigment dispersion methods. In particular, higher color reproducibility and higher luminance as well as higher contrast ratio characteristics are urgently required.
The image sensor is a component for taking an image in a cellular phone camera or a Digital Still Camera (DSC). Image sensors may be classified into charge-coupled devices (CCD) image sensors and Complementary Metal Oxide Semiconductor (CMOS) image sensors depending on manufacturing processes and application methods. Color imaging devices for charge coupled device image sensors or complementary metal oxide semiconductor image sensors include color filters each having filter segments mixing primary colors of red, green, and blue, and the colors are separate. Current color filters installed in color imaging devices have a pattern size of 2 microns or less than 2 microns, which is 1/100 to 1/200 of the pattern size of conventional color filter patterns for LCDs. Therefore, increasing resolution and reducing pattern residues are important factors in determining device performance.
A color filter manufactured by using the pigment-type photosensitive resin composition has limitations in brightness and contrast ratio due to the pigment particle size. In addition, a color image forming apparatus for an image sensor requires a small dispersion particle size to form a fine pattern. In order to meet the demand, attempts have been made to obtain a color filter having improved brightness and contrast ratio by introducing a non-particle-forming dye instead of a pigment to prepare a photosensitive resin composition suitable for the dye. However, the dye has poor durability to the pigment, such as light resistance and heat resistance, and so the brightness may be reduced.
Disclosure of Invention
One embodiment provides a photosensitive resin composition capable of increasing color purity by minimizing the content of a colorant while ensuring durability.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Another embodiment provides a color filter including a photosensitive resin layer.
Another embodiment provides an electronic device including a color filter.
One embodiment provides a photosensitive resin composition comprising a colorant,
wherein the colorant comprises a dye represented by chemical formula 1, a core-shell structure dye, and a phthalocyanine type dye.
[ chemical formula 1]
Figure BDA0003722255810000021
In the chemical formula 1, the first and second,
x is an oxygen atom or a sulfur atom,
L 1 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and
R 1 to R 4 Each independently is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
L 1 Can be represented by the chemical formula L-1.
[ chemical formula L-1]
Figure BDA0003722255810000022
In the chemical formula L-1, the compound,
R 5 and R 6 Each independently a hydrogen atom or a halogen substituted or unsubstituted C1 to C20 alkyl group.
The dye represented by chemical formula 1 may be represented by any one of chemical formulas 1-1 to 1-3.
[ chemical formula 1-1]
Figure BDA0003722255810000031
[ chemical formulas 1-2]
Figure BDA0003722255810000032
[ chemical formulas 1-3]
Figure BDA0003722255810000033
The dye represented by chemical formula 1 may be included in an amount greater than that of the core-shell structure dye, and the dye represented by chemical formula 1 may be included in an amount greater than that of the phthalocyanine type dye.
Phthalocyanine type dyes may be included in an amount greater than the amount of core-shell structure dye.
The dye represented by chemical formula 1 may be included in an amount greater than the content of the core-shell structure dye and the content of the phthalocyanine type dye.
The core-shell structure dye may be composed of a core represented by chemical formula 2 and a shell represented by chemical formula 3.
[ chemical formula 2]
Figure BDA0003722255810000034
In the chemical formula 2, the first and second organic solvents,
R 7 to R 10 Each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
[ chemical formula 3]
Figure BDA0003722255810000041
In the chemical formula 3, the first and second,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group),
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m is an integer of 1 to 10 and,
n is an integer of 1 to 3, and
L 2 and L 3 Each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
The length of the core represented by chemical formula 2 may be 1 to 3 nm.
The core represented by chemical formula 2 may have a maximum absorption peak at a wavelength of 530 nm to 680 nm.
The nucleus represented by chemical formula 2 may be represented by any one of chemical formula 2-1 to chemical formula 2-6.
[ chemical formula 2-1]
Figure BDA0003722255810000042
[ chemical formula 2-2]
Figure BDA0003722255810000043
[ chemical formulas 2-3]
Figure BDA0003722255810000051
[ chemical formulas 2-4]
Figure BDA0003722255810000052
[ chemical formulas 2-5]
Figure BDA0003722255810000053
[ chemical formulas 2 to 6]
Figure BDA0003722255810000054
The shell represented by chemical formula 3 may be represented by chemical formula 3-1.
[ chemical formula 3-1]
Figure BDA0003722255810000061
In the chemical formula 3-1,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group),
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
n is an integer of 1 to 3.
The shell represented by chemical formula 3 may be represented by any one of chemical formulas 3-1-1 to 3-1-3.
[ chemical formula 3-1-1]
Figure BDA0003722255810000071
[ chemical formula 3-1-2]
Figure BDA0003722255810000081
[ chemical formulas 3-1-3]
Figure BDA0003722255810000091
In chemical formulas 3-1-1 to 3-1-3,
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
R 17 and R 18 Each independently a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR = C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group).
The shell represented by chemical formula 3 may have a cage-type width of 6.5 to 7.5 angstroms.
The shell represented by chemical formula 3 may be represented by any one of chemical formula 3-a to chemical formula 3-E.
[ chemical formula 3-A ]
Figure BDA0003722255810000101
[ chemical formula 3-B ]
Figure BDA0003722255810000111
[ chemical formula 3-C ]
Figure BDA0003722255810000121
[ chemical formula 3-D ]
Figure BDA0003722255810000131
[ chemical formula 3-E ]
Figure BDA0003722255810000141
The core-shell structured dye may comprise a core and a shell in a 1.
The phthalocyanine-based dye may be represented by chemical formula 4.
[ chemical formula 4]
Figure BDA0003722255810000151
In the chemical formula 4, the first and second organic solvents,
R 101 to R 116 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 aryloxy group,
provided that R 101 To R 104 At least one of R 105 To R 108 And R 109 To R 112 Are each independently represented by chemical formula 5, and
R 113 to R 116 Is a halogen atom or is represented by chemical formula 5,
[ chemical formula 5]
Figure BDA0003722255810000152
In the chemical formula 5, the reaction mixture is,
R 117 and R 118 Each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substitutedOr unsubstituted C6 to C20 aryl, and
n1 and n2 are each independently an integer of 0 to 5, with the proviso that 1. Ltoreq. N1+ n 2. Ltoreq.5.
Chemical formula 5 may be represented by any one of chemical formula 5-1 to chemical formula 5-4.
[ chemical formula 5-1]
Figure BDA0003722255810000161
[ chemical formula 5-2]
Figure BDA0003722255810000162
[ chemical formulas 5-3]
Figure BDA0003722255810000163
[ chemical formulas 5-4]
Figure BDA0003722255810000164
The colorant may further comprise a pigment.
The colorant may be included in an amount of 1 to 15% by weight, based on the total amount of the photosensitive resin composition.
The photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
The photosensitive resin composition may include 1 to 15% by weight of a colorant, based on the total amount of the photosensitive resin composition; 1 to 20% by weight of a binder resin; 1 to 20% by weight of a photopolymerizable monomer; 0.1 to 10% by weight of a photopolymerization initiator; and the remainder of the solvent.
The photosensitive resin composition may further include malonic acid, 3-amino-1, 2-propanediol, a silane-based coupling agent having a vinyl group or a (meth) acryloyloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Another embodiment provides a color filter including a photosensitive resin layer.
Another embodiment provides an electronic device including a color filter.
Other embodiments of the invention are included in the following detailed description.
The photosensitive resin composition according to the embodiment may have an increased color purity of a green region by mixing and using three different types of dyes, and may additionally ensure durability, which is one of representative problems in using dyes.
Drawings
FIG. 1 is a view of the cage width of the shell represented by chemical formula 3-E.
Detailed Description
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of the claims.
As used herein, "substituted," when a specific definition is not otherwise provided, means that at least one hydrogen of the compound is replaced by a substituent selected from the group consisting of: halogen atoms (F, cl, br, I), hydroxyl groups, C1 to C20 alkoxy groups, nitro groups, cyano groups, amino groups, imino groups, azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamoyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl groups, C6 to C30 aryl groups, C3 to C20 cycloalkyl groups, C3 to C20 cycloalkenyl groups, C3 to C20 cycloalkynyl groups, C2 to C20 heterocycloalkyl groups, C2 to C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, or combinations thereof.
As used herein, "heterocycloalkyl", "heterocycloalkenyl", "heterocycloalkynyl" and "heterocycloalkylene" when a specific definition is not otherwise provided, means that at least one heteroatom of N, O, S or P is present in the cyclic groups of the cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene groups.
As used herein, "(meth) acrylate" refers to both "acrylate" and "methacrylate" when no specific definition is otherwise provided.
As used herein, the term "combination" when a specific definition is not otherwise provided means mixing or copolymerization.
In the chemical formulae of the present specification, unless a specific definition is otherwise provided, when a chemical bond is not drawn at a position that should be given, hydrogen is bonded at the position.
As used herein, "a" indicates a point of bonding to the same or different atom or chemical formula when a specific definition is not otherwise provided.
The photosensitive resin composition according to an embodiment includes a colorant, wherein the colorant includes a dye represented by chemical formula 1, a core-shell structure dye, and a phthalocyanine type dye.
[ chemical formula 1]
Figure BDA0003722255810000181
In the chemical formula 1, the first and second,
x is an oxygen atom or a sulfur atom,
L 1 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and
R 1 to R 4 Each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
The CMOS image sensor refers to a non-memory semiconductor that converts an image received by a camera into a digital signal and is manufactured through the same CMOS semiconductor process as a DRAM. The CMOS image sensor has a pixel polymerization structure of a color filter, a photodiode, an amplifier, and the like, and in order to realize a high-definition and ultra-thin camera module, it is important to secure a color filter technology. Color filter technology requires high resolution and high sensitivity materials, where both properties can be satisfied by cutting a specific wavelength that can control the properties and sensitivity of a negative photoresist.
In order to cut a specific wavelength, a conventional technique of controlling the wavelength by selecting the most similar pigment to increase the ratio has been used, but the content of the colorant in the photoresist increases and thus the workability and reliability are reduced, mainly not applicable to an actual process or to meet desired characteristics.
The present invention relates to a photosensitive resin composition which improves the above problems and has desired cutting characteristics. Specifically, the photosensitive resin composition of the present invention can increase the color purity of green by adjusting and cutting the wavelength of the dye represented by chemical formula 1 to cut a blue-green region between blue and green, and also applying the dye having a core-shell structure to cut a yellow region between green and blue. Further, two types of dyes may be used together with a phthalocyanine type dye to ensure durability. Also, the combination of three types of dyes may reduce the use of colorants.
In other words, the photosensitive resin composition according to the embodiment can ensure workability and reliability at a thin thickness by using a small amount of colorant through a combination of specific dyes, and thus is optimally used for a process material of LCD and CIS to increase a color gamut without decreasing transmittance, which may not be much different from the conventional art.
For example, in chemical formula 1, L1 may be represented by chemical formula L-1.
[ chemical formula L-1]
Figure BDA0003722255810000182
In the chemical formula L-1, the compound,
R 5 and R 6 Each independently a hydrogen atom or a halogen substituted or unsubstituted C1 to C20 alkyl group.
For example, the dye represented by chemical formula 1 may be represented by any one of chemical formulas 1-1 to 1-3, but is not limited thereto.
[ chemical formula 1-1]
Figure BDA0003722255810000191
[ chemical formulas 1-2]
Figure BDA0003722255810000192
[ chemical formulas 1-3]
Figure BDA0003722255810000193
For example, the dye represented by chemical formula 1 may be included in an amount greater than that of the core-shell structure dye, and the dye represented by chemical formula 1 may be included in an amount greater than that of the phthalocyanine type dye. In this case, color purity and durability can be ensured at the same time.
In addition, phthalocyanine type dyes may be included in an amount greater than the amount of core-shell structure dye. Specifically, the dye represented by chemical formula 1 may be included in an amount greater than the amount of the phthalocyanine-based dye, the phthalocyanine-based dye may be included in an amount greater than the amount of the core-shell structure dye, and the dye represented by chemical formula 1 may be included in an amount greater than the mixed content of the core-shell structure dye and the phthalocyanine-based dye. In this case, it may be more advantageous to ensure both color purity and durability.
For example, the core-shell structure dye may be composed of a core represented by chemical formula 2 and a shell represented by chemical formula 3.
[ chemical formula 2]
Figure BDA0003722255810000194
In the chemical formula 2, the first and second organic solvents,
R 7 to R 10 Each independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl,
[ chemical formula 3]
Figure BDA0003722255810000201
In the chemical formula 3, the first and second,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group),
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m is an integer of 1 to 10,
n is an integer of 1 to 3, and
L 2 and L 3 Each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
For example, the core-shell structure dye may include a non-covalent bond, that is, a hydrogen bond between an oxygen atom of the compound represented by chemical formula 2 and a hydrogen atom forming a bond with a nitrogen atom of the shell represented by chemical formula 3.
The compound represented by chemical formula 2 has excellent green spectral characteristics and a high molar extinction coefficient, and thus may be used as a green dye, but has a problem of deteriorating brightness due to inferior durability during baking after forming a color resist as compared to a pigment. In an embodiment, since the shell represented by chemical formula 3 may form a core-shell structure with the core represented by the compound represented by chemical formula 2, the core-shell structure compound may improve durability of a color filter applied as a colorant, realizing a color filter having high brightness and high contrast.
Specifically, the core-shell structure dye has a structure in which a compound represented by chemical formula 2 is a core and a shell surrounds the core, wherein the shell is a macrocyclic compound represented by chemical formula 3 and can form a coating layer while surrounding the core. Such a structure (i.e., a structure in which the compound represented by chemical formula 2 exists inside the ring represented by chemical formula 3) may improve the durability of the core-shell structure dye, realizing a color filter having high brightness and high contrast.
For example, in chemical formula 3, L2 and L3 may each independently be a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is improved, and a structure in which the shell surrounds the compound represented by chemical formula 2 is easily formed.
For example, in chemical formula 2, R 7 And R 9 May each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 8 And R 10 Each independently may be a substituted or unsubstituted C6 to C20 aryl group.
For example, R 7 And R 9 May each independently be 'C1 to C20 alkyl substituted or unsubstituted with C1 to C10 alkoxy' or 'C3 to C20 cycloalkyl substituted or unsubstituted with C1 to C10 alkoxy', and R 8 And R 10 May each independently be 'C6 to C20 aryl substituted or unsubstituted with C1 to C10 alkoxy'.
For example, the C1 to C10 alkoxy group may be an unsubstituted C1 to C10 alkoxy group or a C1 to C6 alkoxy group substituted with a C1 to C4 alkyl group.
As shown in the following scheme, the compound represented by chemical formula 2 has three resonance structures, but in the present specification, only one resonance structure is shown for the compound represented by chemical formula 2 for convenience. That is, the compound represented by chemical formula 2 may be represented by any one of three resonance structures.
[ solution ]
Figure BDA0003722255810000211
For example, the core may be represented by any one of chemical formula 2-1 to chemical formula 2-6, but is not necessarily limited thereto.
[ chemical formula 2-1]
Figure BDA0003722255810000212
[ chemical formula 2-2]
Figure BDA0003722255810000213
[ chemical formulas 2-3]
Figure BDA0003722255810000221
[ chemical formulas 2-4]
Figure BDA0003722255810000222
[ chemical formulas 2 to 5]
Figure BDA0003722255810000223
[ chemical formulas 2 to 6]
Figure BDA0003722255810000231
For example, when the compounds represented by chemical formulas 2-1 to 2-6 are used in a photosensitive resin composition (e.g., as a dye), the solubility of a solvent to be described later may be greater than or equal to 5, such as 5 to 10. The solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent. When the compound (e.g., dye) has a solubility within the range, compatibility with other components (i.e., a binder resin, a photopolymerizable monomer, and a photopolymerization initiator described later) in the photosensitive resin composition and coloring properties can be ensured, and precipitation of the dye can be prevented.
For example, the compounds represented by chemical formulas 2-1 to 2-6 may have improved heat resistance. That is, the thermal decomposition temperature measured using a thermogravimetric analyzer (TGA) may be greater than or equal to 200 deg.C, such as 200 deg.C to 300 deg.C.
The length of the compound represented by chemical formula 2 included in or composed of the core may be 1 to 3 nm, for example, 1.5 to 2 nm. When the compound represented by chemical formula 2 has a length within the range, the core-shell structure may be easily formed. In other words, the compound represented by chemical formula 2 has a length within the range and thus a structure in which the compound represented by chemical formula 2 is surrounded by a shell, which is a macrocyclic compound represented by chemical formula 3, can be easily formed. When a compound having a length outside the range is used, a structure in which the shell does not surround the core compound may not be obtained, and durability may not be improved.
For example, the core-shell structured compound may have a maximum absorption peak at a wavelength of 530 nanometers to 680 nanometers. The core-shell structured dye having spectral characteristics is used, for example, as a green dye and thus can provide a photosensitive resin composition for a color filter having high brightness and high contrast.
For example, the core-shell structure compound may comprise a core and a shell in a 1. When the core and the shell are present in the molar ratio, the coating layer (shell) surrounding the core can be formed well.
For example, the shell represented by chemical formula 3 may be represented by chemical formula 3-1.
[ chemical formula 3-1]
Figure BDA0003722255810000241
In the chemical formula 3-1, the,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group),
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
n is an integer of 1 to 3.
For example, in chemical formula 3-1, R 11 Can be a hydrogen atom, and R 12 To R 15 May each independently be a hydrogen atom or a substituted or halogen atom.
For example, in chemical formula 3-1, R 11 May be a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group, OR a-C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group), and R 12 To R 15 May each independently be a hydrogen atom.
For example, R 11 May be a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR = C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 to C20 alkyl group), and R 12 To R 15 Is a substituted or unsubstituted C1 to C20 alkyl group.
For example, the shell represented by chemical formula 3 may be represented by any one of chemical formulas 3-1-1 to 3-1-3.
[ chemical formula 3-1-1]
Figure BDA0003722255810000251
[ chemical formula 3-1-2]
Figure BDA0003722255810000261
[ chemical formulas 3-1-3]
Figure BDA0003722255810000271
In chemical formulas 3-1-1 to 3-1-3,
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
R 17 and R 18 Each independently a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR = C (= O) OR 16 (R 16 Is a substituted or unsubstituted C1 toA C20 alkyl group).
For example, the shell may have a cage width of 6.5 to 7.5 angstroms and a volume of 10 to 16 angstroms. The cage width refers to an internal distance of the shell in the present disclosure, for example, a distance between two different phenylene groups in which two methylene groups are bonded in the shell represented by chemical formula 3 (see fig. 1). When the shell has a cage-type width within the range, a core-shell dye having a structure surrounding the arylcyanine based compound can be obtained, and thus when the core-shell dye is used as a colorant for the photosensitive resin composition, a color filter having improved durability and high luminance can be implemented.
For example, the shell may be represented by any one of chemical formulas 3-A to 3-E, but is not necessarily limited thereto.
[ chemical formula 3-A ]
Figure BDA0003722255810000281
[ chemical formula 3-B ]
Figure BDA0003722255810000291
[ chemical formula 3-C ]
Figure BDA0003722255810000301
[ chemical formula 3-D ]
Figure BDA0003722255810000311
[ chemical formula 3-E ]
Figure BDA0003722255810000321
For example, the core-shell structure dye may be represented by the formula A-1 or the formula A-2, but is not necessarily limited thereto.
[ chemical formula A-1]
Figure BDA0003722255810000322
[ chemical formula A-2]
Figure BDA0003722255810000331
The core-shell dyes can be used alone as green dyes and can also be mixed with auxiliary dyes.
The auxiliary dye may be triarylmethane-based dye, anthraquinone-based dye, benzylidene-based dye, cyanine-based dye, phthalocyanine-based dye, azaporphyrin-based dye, indigo-based dye, xanthene-based dye, pyridone azo-based dye, or the like.
For example, the phthalocyanine-based dye may be represented by chemical formula 4.
[ chemical formula 4]
Figure BDA0003722255810000332
In the chemical formula 4, the first and second organic solvents,
R 101 to R 116 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 aryloxy group,
provided that R is 101 To R 104 At least one of R 105 To R 108 And R 109 To R 112 Are each independently represented by chemical formula 5, and
R 113 to R 116 Is a halogen atom or is represented by chemical formula 5,
[ chemical formula 5]
Figure BDA0003722255810000341
Wherein, in chemical formula 5,
R 117 and R 118 Each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group, and
n1 and n2 are each independently an integer of 0 to 5, with the proviso that 1. Ltoreq. N1+ n 2. Ltoreq.5.
For example, chemical formula 5 may be represented by any one of chemical formula 5-1 to chemical formula 5-4.
[ chemical formula 5-1]
Figure BDA0003722255810000342
[ chemical formula 5-2]
Figure BDA0003722255810000343
[ chemical formulas 5-3]
Figure BDA0003722255810000351
[ chemical formulas 5-4]
Figure BDA0003722255810000352
For example, the phthalocyanine-based dye may be represented by any one of chemical formula 6 to chemical formula 8, but is not necessarily limited thereto.
[ chemical formula 6]
Figure BDA0003722255810000353
[ chemical formula 7]
Figure BDA0003722255810000354
[ chemical formula 8]
Figure BDA0003722255810000361
The colorant may further comprise a pigment.
The pigment may be red pigment, green pigment, blue pigment, yellow pigment, black pigment, etc.
Examples of the red pigment may be c.i. red pigment 254, c.i. red pigment 255, c.i. red pigment 264, c.i. red pigment 270, c.i. red pigment 272, c.i. red pigment 177, c.i. red pigment 89, and the like. Examples of the green pigment may be c.i. green pigment 7, c.i. green pigment 36, c.i. green pigment 58, c.i. green pigment 59, and the like. Examples of the blue pigment may be copper phthalocyanine pigments such as c.i. blue pigment 15. Examples of the yellow pigment may be isoindoline-based pigments such as c.i. yellow pigment 139 and the like; quinoline yellow pigments such as c.i. yellow pigment 138 and the like; nickel complex pigments such as c.i. yellow pigment 150 and the like. Examples of black pigments may be aniline black, perylene black, titanium black, carbon black, and the like. The pigments may be used alone or in a mixture of two or more and are not limited thereto.
The pigment may be contained in the photosensitive resin composition for a color filter in a pigment dispersion state. The pigment dispersion liquid may be composed of a pigment and a solvent, a dispersant, a dispersion resin, and the like.
The solvent may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like, and desirably is propylene glycol methyl ether acetate.
The dispersant aids in uniform dispersion of the pigment and may comprise a nonionic dispersant, an anionic dispersant or a cationic dispersant. Specific examples may be polyalkylene glycol or an ester thereof, polyoxyalkylene, polyol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkylamide alkylene oxide adduct, alkylamine, and may be used alone or in a mixture of two or more.
The dispersion resin may be an acrylic resin containing a carboxyl group, and improves the stability of the pigment dispersion and the pattern properties of the pixels.
However, the colorant in the photosensitive resin composition according to the embodiment may be composed of the above three types of dyes alone, and durability deterioration may not occur, as compared to the case where a pigment is additionally included. That is, when the colorant is composed of three types of dyes alone without using a pigment, the amount of the colorant used can be greatly reduced, so that workability and reliability can be ensured even at a thin thickness.
The colorant may be included in an amount of 1 to 15 wt%, such as 1 to 10 wt%, such as 1 to 5 wt%, such as 1 to 3 wt%, based on the total amount of the photosensitive resin composition. When the colorant in the above range is used, higher brightness and contrast can be exhibited in desired color coordinates.
The photosensitive resin composition according to the embodiment may further include a binder resin.
The binder resin may be a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit (acrylic binder resin).
The first ethylenically unsaturated monomer may be an ethylenically unsaturated monomer including one or more carboxyl groups, and specific examples thereof may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt%, for example 10 to 40 wt%, based on the total amount of the alkali soluble resin.
The second ethylenically unsaturated monomer may include aromatic vinyl compounds such as styrene, alpha-methylstyrene, vinyltoluene and vinylbenzyl methyl ether; unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; vinyl cyanide compounds such as (meth) acrylonitrile; unsaturated amide compounds such as (meth) acrylamide and the like, and these may be used alone or in combination of two or more.
Specific examples of the binder resin may be a methacrylic acid/benzyl methacrylate copolymer, a methacrylic acid/benzyl methacrylate/styrene copolymer, a methacrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, a methacrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, etc., but the present invention is not limited thereto. These may be used alone or in a mixture of two or more.
The weight average molecular weight of the binder resin may be 3,000 g/mole to 150,000 g/mole, such as 5,000 g/mole to 50,000 g/mole, such as 20,000 g/mole to 30,000 g/mole. When the binder resin has a weight average molecular weight within the range, the composition may have excellent close contact properties with the substrate, good physical and chemical properties, and appropriate viscosity.
The binder resin may have an acid value of 15 mg KOH/g to 60 mg KOH/g, such as 20 mg KOH/g to 50 mg KOH/g. When the binder resin has an acid value within the range, it may bring excellent pixel resolution.
The binder resin may further include epoxy-based binder resins as well as acrylic binder resins.
The epoxy-based binder resin is a monomer or an oligomer polymerizable by heating, and may include a compound having a carbon-carbon unsaturated bond and a carbon-carbon ring bond.
The epoxy-based binder resin may further include bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, phenol novolac-type epoxy resin, cyclic aliphatic epoxy resin, and aliphatic polyglycidyl ether.
Currently available products of the Epoxy-based binder resin may include YX4000, YX4000H, YL6121H, YL6640, or YL6677 of oiled Shell Epoxy co., ltd; cresol novolac type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 of Nippon Kayaku Co., ltd., and EPIKOTE 180S75 of oiled Shell epoxy resin Co., ltd.; bisphenol A epoxy resins such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE1010 and EPIKOTE 828 of OKI Shell epoxy resin Co., ltd; bisphenol F type epoxy resins such as EPIKOTE 807 and EPIKOTE 834 from oiled shell epoxy resin co; phenol novolac type epoxy resins such as EPIKOTE 152, EPIKOTE 154 or EPIKOTE 157H65 from oil shell epoxy resin co., EPIKOTE and EPPN 201, EPPN 202 from japan chemical co., ltd; other cyclic aliphatic epoxy resins, such as CY175, CY177 and CY179 of CIBA-cargyl corporation (CIBA-GEIGY a.g), ERL-4234, ERL-4299, ERL-4221 and ERL-4206 of united states co-charring corporation (u.c.c.), shodyne 509 of Showa Denko k.k., ARALDITE CY-182, CY-192 and CY-184 of CIBA-cargyl corporation, epichron 200 and Epichron 400 of Dainippon Ink chemical co., ltd. (Dainippon Ink and Chemicals, inc.), epiike ik 872, epote and EP1032, celike coating 872 and 5661 of selan-taeni corporation; aliphatic polyglycidyl ethers such as EPIKOTE 190P and EPIKOTE 191P from oiled shell epoxy resin co, epolite 100MF from Kyoesha Yushi co., ltd., and Epiol TMP from Nippon Yushi co., ltd., and the like.
The binder resin may be included in an amount of 1 to 20 wt%, for example, 1 to 15 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, developability is improved in manufacturing a color filter, and crosslinking properties are improved to obtain excellent surface smoothness.
The photosensitive resin composition according to the embodiment may further include a photopolymerizable monomer.
The photopolymerizable monomers may be monofunctional or polyfunctional esters of (meth) acrylic acid having at least one ethylenically unsaturated double bond.
Since the photopolymerizable monomer has an ethylenically unsaturated double bond, a pattern having improved heat resistance, light resistance, and chemical resistance can be formed by causing sufficient polymerization during exposure to light in the pattern forming process.
Specific examples of the photopolymerizable monomer may be ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol a epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, and the like.
Commercially available examples of the photopolymerizable monomers are as follows. The monofunctional (meth) acrylate may comprise anixox
Figure BDA0003722255810000381
Figure BDA0003722255810000382
(Toagosei Chemistry Industry Co., ltd.); kayalard
Figure BDA0003722255810000383
(Nippon Kagaku Co., ltd.);
Figure BDA0003722255810000384
(Osaka Organic Chemical Co., ltd. (Osaka Organic Chemical Ind., ltd.)) and the like. Examples of difunctional (meth) acrylates may include anixox
Figure BDA0003722255810000385
(Toya Synthesis chemical Co., ltd.) Kayarad
Figure BDA0003722255810000386
Figure BDA0003722255810000387
(Nippon Kagaku Co., ltd.),
Figure BDA0003722255810000388
V-335
Figure BDA0003722255810000389
(Osaka organic chemical Co., ltd.) and the like. Examples of the trifunctional (meth) acrylate may include Anixx available from Toyo chemical Co., ltd
Figure BDA00037222558100003810
Figure BDA00037222558100003811
Etc.; kayalard of Nippon chemical Co., ltd
Figure BDA00037222558100003812
Figure BDA00037222558100003813
Osaka Yucheng Chiense Kogyo Co., ltd(Osaka Yuki Kayaku Kogyo Co. Ltd.)
Figure BDA00037222558100003814
And so on. These may be used alone or in the form of a mixture of two or more.
The photopolymerizable monomers may be treated with an acid anhydride to improve developability.
The photopolymerizable monomer may be included in an amount of 1 to 20 wt%, or, for example, 1 to 15 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, pattern characteristics and developability may be improved when the color filter is manufactured.
The photosensitive resin composition according to the embodiment may further include a photoinitiator.
The photopolymerization initiator may include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like.
Examples of the acetophenone compounds may be 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like.
Examples of the benzophenone-based compound may be benzophenone, benzoyl benzoate, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone and the like.
Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.
Examples of benzoin-based compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.
Examples of the triazine-based compound may be 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4 '-methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-biphenyl-4, 6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2-4-trichloromethyl (4' -methoxystyryl) -6-triazine and the like.
Examples of the oxime compounds may be 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione, 1- (o-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone, and the like.
The photopolymerization initiator may further contain, in addition to the compound, a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, a diazonium-based compound, an imidazole-based compound, a bisimidazole-based compound, a fluorene-based compound, and the like.
The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight, or for example, 0.1 to 5% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization is sufficiently generated during exposure in a pattern forming process for manufacturing a color filter, thereby improving sensitivity and improving transmittance.
The photosensitive resin composition according to the embodiment may further include a solvent.
The solvent is not particularly limited, but specifically, for example, alcohols such as methanol, ethanol and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and the like; glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, and the like; cellosolve acetates such as cellosolve methyl acetate, cellosolve ethyl acetate, cellosolve diethyl acetate, and the like; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactate such as methyl lactate, ethyl lactate, etc.; alkyl glycolates such as methyl glycolate, ethyl glycolate, butyl glycolate, etc.; alkoxyalkyl acetates such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, and the like; alkyl 3-hydroxypropionates such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropionates such as methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and the like; alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, and the like; or ketoesters such as ethyl pyruvate and the like, and further may be N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone (isophorone), hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate, propylene carbonate, cellosolve phenyl acetate, and they may be used alone or in a mixture of two or more.
In view of compatibility and reactivity, it is desirable to use: glycol ethers such as ethylene glycol monoethyl ether and the like; ethylene glycol alkyl ether acetates such as ethylene glycol ethyl ether acetate and the like; esters, such as 2-hydroxyethyl propionate and the like; diethylene glycols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.
The solvent may be contained in the balance, and specifically, 35 to 90% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained in the above range, the photosensitive resin composition has excellent applicability and can maintain excellent flatness in a film having a thickness of 3 micrometers or more than 3 micrometers.
The photosensitive resin composition may further comprise other additives such as malonic acid; 3-amino-1, 2-propanediol; a silane-based coupling agent containing a vinyl group or a (meth) acryloyloxy group; a leveling agent; a fluorine-based surfactant; a radical polymerization initiator to prevent stains or spots during coating, to adjust leveling, or to prevent pattern residues due to non-development.
The photosensitive resin composition may further include an epoxy compound to improve close contact property with the substrate.
Examples of the epoxy compound include a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol a type epoxy compound, an alicyclic epoxy compound, or a combination thereof.
The amount of additive used can be controlled depending on the desired properties.
Another embodiment provides a photosensitive resin layer produced by using the photosensitive resin composition.
Another embodiment provides a color filter manufactured using the photosensitive resin composition. The method of manufacturing the color filter is as follows.
A protective layer (SiN) of 500 to 1500 angstroms thickness is coated on or over a bare glass substrate using a suitable method such as spin coating, slit coating, or the like x ) On a glass substrate to be used for coloringThe photosensitive resin composition of the optical filter is coated to have a thickness of 3.1 to 3.4 micrometers. After coating, the composition is irradiated with light to form a desired pattern of a color filter. After the irradiation of light, the coating layer is treated with an alkaline developer, and a non-irradiated region thereof may be dissolved, thereby forming a pattern for a color filter. This process is repeated depending on the number of R, G, and B colors required, thereby manufacturing a color filter having a desired pattern.
In addition, the image pattern obtained by development is cured by heat treatment, actinic ray irradiation, or the like, thus improving crack resistance, solvent resistance, or the like.
Another embodiment provides an electronic device, such as a display device, a camera, etc., including a color filter.
Hereinafter, the present invention is shown in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the invention in any way.
(preparation of dye)
( Preparation example 1: preparation of the Compound represented by chemical formula 1-1 )
8.15 mmol of 7- (diethylamino) -2-oxo-2H-benzopyran-3-carbaldehyde, 4.08 mmol of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 163 mmol of sodium acetate were dissolved in 40 ml of acetic acid and then stirred at 90 ℃ for 10 hours. Subsequently, 200 ml of water was added to the reaction mixture. The precipitate produced therein was filtered and dissolved in dichloromethane, and then washed with water through a separatory funnel.
The dichloromethane layer recovered from the separatory funnel was MgSO 4 Dried and purified by silica gel column chromatography to obtain the compound represented by chemical formula 1-1.
[ chemical formula 1-1]
Figure BDA0003722255810000411
Maldi-tof MS：816m/z
( Preparation example 2: preparation of the Compound represented by chemical formula 1-2 )
A compound represented by chemical formula 1-2 was obtained in the same manner as in preparation example 1, except that 7- (4- (2-isobutyl-2, 4-dimethylphenyl) amino) -2-oxo-2H-benzopyran-3-carbaldehyde was used instead of 7- (diethylamino) -2-oxo-2H-benzopyran-3-carbaldehyde.
[ chemical formulas 1-2]
Figure BDA0003722255810000412
Maldi-tof MS：1024m/z
( Preparation example 3: preparation of Compounds represented by chemical formulas 1 to 3 )
A compound represented by chemical formula 1-3 was obtained in the same manner as in preparation example 1, except that 7- (4-diphenylamino) -2-oxo-2H-benzopyran-3-carbaldehyde was used instead of 7- (diethylamino) -2-oxo-2H-benzopyran-3-carbaldehyde.
[ chemical formulas 1-3]
Figure BDA0003722255810000413
Maldi-tof MS：1008m/z
( Preparation example 4: preparation of Compounds represented by chemical formulas 1 to 4 )
2, 4-dimethyldiphenylamine (10 moles), 1, 2-epoxycyclohexane (12 moles) and sodium hydride (12 moles) were added to N, N-dimethylformamide, and then stirred at 90 ℃ for 24 hours. Then, an additional 15 mmol of iodomethyl group was added thereto, and then stirred for 3 hours.
Subsequently, ethyl acetate was added to the solution and then washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and separated by column chromatography, thereby obtaining the compound of intermediate 1.
Intermediate 1 (60 mmol), 3, 4-dihydroxy-3-cyclobutyne-1, 2-dione (30 mmol) were taken up in toluene (200 ml) and butanol (200 ml) and then refluxed, and the resulting water was removed with Dean-stark distillation apparatus. After stirring for 12 hours, the green reaction product was distilled under reduced pressure and purified by column chromatography to obtain the compound of intermediate 2.
After intermediate 2 (5 mmol) was dissolved in 600 ml of chloroform solvent, triethylamine (50 mmol) was added thereto, and then 2, 6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were respectively dissolved in 60 ml of chloroform, and then simultaneously added dropwise thereto at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated by column chromatography, thereby obtaining the compound represented by chemical formula a-1.
[ chemical formula A-1]
Figure BDA0003722255810000421
Maldi-tof MS：1231m/z
( Preparation example 5: preparation of Compounds represented by chemical formulas 1 to 5 )
The same synthesis as above was carried out until intermediate 2 of formula a-1. After intermediate 2 (5 mmol) was dissolved in 600 ml of chloroform solvent, triethylamine (50 mmol) was added thereto, and then 2, 6-pyridinedicarbonyl dichloride (20 mmol) and tetrafluoro-p-xylylenediamine (20 mmol) were respectively dissolved in 60 ml of chloroform and simultaneously added dropwise thereto at room temperature for 5 hours. After 12 hours, the obtained mixture was distilled under reduced pressure and separated by column chromatography, thereby obtaining a compound represented by chemical formula a-2.
[ chemical formula A-2]
Figure BDA0003722255810000422
Maldi-tof MS：1375m/z
( Preparation example 6: preparation of Compounds represented by chemical formulas 1 to 6 )
3,4,5, 6-tetrachlorophthalonitrile (5 g), 2, 4-di-tert-butylphenol (3.8 g), K 2 CO 3 (3.898G) and N, N-dimethylformamide (50 ml) were placed in a 100 ml flask and then stirred at 70 ℃. When the reaction was completed, after extraction with Ethyl Acetate (EA), the liquid column purified by EA/hexane column chromatography was concentrated to obtain a solid, and the solid was dried in vacuum, thereby obtaining 3,5, 6-trichloro-4- (2, 4-di-tert-butylphenoxy) -phthalonitrile.
3,5, 6-trichloro-4- (2, 4-di-tert-butylphenoxy) -phthalonitrile (1.45 g), 1, 8-diazabicycloundecen-7-ene (0.38 g) and 1-pentenol (7 g) were placed in a 100 ml flask and heated at 90 ℃, and after the solids dissolved, zinc acetate (0.15 g) was added thereto, and then stirred while continuing heating to 140 ℃. When the reaction was complete, the precipitate was filtered with MeOH and dried in vacuo. The dried solid was purified by column chromatography. A small amount of methylene chloride was added to the obtained solid, and after the solid therein was dissolved, methanol was added thereto to conduct crystallization. The obtained solid was filtered and dried in vacuum, thereby obtaining the compound represented by chemical formula 6.
[ chemical formula 6]
Figure BDA0003722255810000431
Maldi-tof MS：1809m/z
( Preparation example 7: preparation of Compounds represented by chemical formulas 1 to 7 )
3,4,5, 6-tetrachlorophthalonitrile (5 g), 2-phenylphenol (3.21 g), K 2 CO 3 (3.9 g) and acetone (25 ml) were placed in a 100 ml flask and then stirred while heating at 70 ℃. When the reaction was completed, the resultant was filtered and washed with acetone, and a solid obtained by distilling a liquid therefrom was dissolved in a small amount of dichloromethane, washed several times with hexane, filtered and dried in vacuum, thereby obtaining 4- (biphenyl-2-yloxy) -3,5, 6-trichloro-phthalonitrile.
4- (biphenyl-2-yloxy) -3,5, 6-trichloro-phthalonitrile (1.6 g), 3,4, 6-trichloro-5- (2, 6-dichloro-phenoxy) -phthalonitrile (1.5 g), 1, 8-diazabicycloundec-7-ene (1.74 g) and 1-pentenol (14 g) were placed in a 100 ml flask and heated at 90 ℃, and after the solids dissolved, zinc acetate (0.34 g) was added thereto, and stirring was then carried out while heating at 140 ℃. When the reaction was complete, the precipitate was confirmed with methanol, filtered, dried in vacuo, and purified by column chromatography. Subsequently, an appropriate amount of dichloromethane was added to the purified solid, and methanol was added thereto to perform crystallization. The crystalline solid was filtered and dried in vacuum, thereby obtaining the compound represented by chemical formula 7.
[ chemical formula 7]
Figure BDA0003722255810000432
Maldi-tof MS：1650m/z
( Preparation example 8: preparation of Compounds represented by chemical formulas 1 to 8 )
3,4,5, 6-tetrachlorophthalonitrile (5 g), 2-cyclohexylphenol (3.3143 g), K 2 CO 3 (3.898 g) and N, N-dimethylformamide (50 ml) were placed in a 100 ml flask and then stirred while heating at 70 ℃. When the reaction was completed, after extraction with Ethyl Acetate (EA), the liquid purified by EA/hexane column chromatography was concentrated, and the solid obtained therefrom was dried in vacuo, thereby obtaining a compound of 3,5, 6-trichloro-4- (2-cyclohexylphenoxy) -phthalonitrile.
In a 100 ml flask, 3,5, 6-trichloro-4- (2-cyclohexylphenoxy) -phthalonitrile (1.5 g), 3,4,5, 6-tetrachlorophthalonitrile (0.33 g), 1, 8-diazabicycloundecen-7-ene (1.3 g) and 1-pentenol (15 ml) were heated at 90 ℃, and after the solid was dissolved, zinc acetate (0.23 g) was added thereto, and then stirring was performed while continuously heating at 140 ℃. When the reaction was complete, the precipitate was filtered with MeOH and dried in vacuo, and the dried solid was purified by column chromatography. Subsequently, a small amount of dichloromethane was added to the purified solid to dissolve it, and methanol was added thereto to perform crystallization. The obtained solid was filtered and dried in vacuum, thereby obtaining the compound represented by chemical formula 8.
[ chemical formula 8]
Figure BDA0003722255810000441
Maldi-tof MS：1548m/z
(preparation of photosensitive resin composition)
The specifications of the components used for preparing the photosensitive resin composition are as follows.
(A) Colouring agent
(dyes)
(A1) The dye (represented by chemical formula 1-1) prepared in preparation example 1
(A2) The dye (represented by chemical formula 1-2) prepared in preparation example 2
(A3) The dyes prepared in preparation example 3 (represented by chemical formulas 1 to 3)
(A4) The dye prepared in preparation example 4 (represented by chemical formula A-1)
(A5) The dye prepared in preparation example 5 (represented by formula A-2)
(A6) The dye (represented by chemical formula 6) prepared in preparation example 6
(A7) The dye (represented by chemical formula 7) prepared in preparation example 7
(A8) The dye (represented by chemical formula 8) prepared in preparation example 8
(pigment)
(A9) C.i. green pigment 58 (SANYO)
(A10) C.i. yellow pigment 138 (sanyang)
(B) Adhesive resin
(B1) Acrylic adhesive resin (RY 25, SHOWA DENKO)
(B2) Epoxy adhesive resin (EHPE 3150, dailn (DAICEL))
(C) Photopolymerizable monomers
Dipentaerythritol hexaacrylate (Nippon Kabushiki Kaisha)
(D) Photopolymerization initiator
SPI-03 (Samyang Corp.)
(E) Solvent(s)
Propylene Glycol Monomethyl Ether Acetate (PGMEA)
Examples 1 to 6 and comparative examples 1 to 4
Each of the photosensitive resin compositions was prepared by mixing the components in the compositions shown in table 1. Specifically, a photopolymerization initiator was dissolved in a solvent and then stirred at room temperature for 2 hours, a colorant was added thereto and then stirred for 30 minutes, and a binder resin and a photopolymerizable monomer were added thereto and then stirred at room temperature for 2 hours. The resulting solution was filtered 3 times to remove impurities, and each photosensitive resin composition was prepared.
(Table 1)
(Unit:% by weight)
Figure BDA0003722255810000451
(evaluation)
Evaluation of reliability
The photosensitive resin compositions according to examples 1 to 6 and comparative examples 1 to 4 were coated to a thickness of 1 to 3 micrometers, respectively, on a degreased and cleaned glass substrate having a thickness of 1 mm, and dried on a hot plate at 90 ℃ for 2 minutes, thereby obtaining films. Subsequently, the film was exposed using a high-pressure mercury lamp having a dominant wavelength of 365 nm, dried in an oven at 200 ℃ for 60 hours, and then the thickness and the transmittance were measured using a contact type measuring instrument (electrooptic) and MCPS measuring instruments, and the results are shown in table 2.
(Table 2)
Figure BDA0003722255810000452
Referring to table 2, it can be easily expected that the photosensitive resin compositions according to the examples have improved transmittance even at a thin thickness, so that workability and reliability are improved, and color gamut is also improved because there is no reduction in transmittance.
While the invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The foregoing embodiments are therefore to be considered in all respects illustrative rather than limiting of the invention.

Claims (25)

1. A photosensitive resin composition comprising a colorant,
wherein the colorant comprises a dye represented by chemical formula 1, a core-shell structure dye, and a phthalocyanine-based dye:
[ chemical formula 1]
Figure FDA0003722255800000011
Wherein, in chemical formula 1,
x is an oxygen atom or a sulfur atom,
L 1 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, and
R 1 to R 4 Each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
2. The photosensitive resin composition according to claim 1, wherein
L 1 Represented by the formula L-1:
[ chemical formula L-1]
Figure FDA0003722255800000012
Wherein, in the chemical formula L-1,
R 5 and R 6 Each independently a hydrogen atom or a halogen substituted or unsubstituted C1 to C20 alkyl group.
3. The photosensitive resin composition according to claim 1, wherein
The dye represented by chemical formula 1 is represented by any one of chemical formulae 1-1 to 1-3:
[ chemical formula 1-1]
Figure FDA0003722255800000013
[ chemical formulas 1-2]
Figure FDA0003722255800000021
[ chemical formulas 1-3]
Figure FDA0003722255800000022
4. The photosensitive resin composition according to claim 1, wherein
The dye represented by chemical formula 1 is included in an amount greater than that of the core-shell structure dye, and
the dye represented by chemical formula 1 is included in an amount greater than that of the phthalocyanine-based dye.
5. The photosensitive resin composition according to claim 4, wherein
The phthalocyanine-based dye is included in an amount greater than the amount of the core-shell structure dye.
6. The photosensitive resin composition according to claim 1, wherein
The dye represented by chemical formula 1 is included in an amount greater than a mixed content of the core-shell structure dye and the phthalocyanine type dye.
7. The photosensitive resin composition according to claim 1, wherein
The core-shell structure dye is composed of a core represented by chemical formula 2 and a shell represented by chemical formula 3:
[ chemical formula 2]
Figure FDA0003722255800000023
Wherein, in chemical formula 2,
R 7 to R 10 Each independently substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, or substituted or unsubstituted C6 to C20 aryl,
[ chemical formula 3]
Figure FDA0003722255800000031
Wherein, in chemical formula 3,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 Wherein R is 16 Is a substituted or unsubstituted C1 to C20 alkyl group,
R 12 to R 15 Each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
m is an integer of 1 to 10,
n is an integer of 1 to 3, and
L 2 and L 3 Each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
8. The photosensitive resin composition according to claim 7, wherein
The length of the core represented by chemical formula 2 is 1 to 3 nm.
9. The photosensitive resin composition according to claim 7, wherein
The core represented by chemical formula 2 has a maximum absorption peak at a wavelength of 530 nm to 680 nm.
10. The photosensitive resin composition according to claim 7, wherein
The core represented by chemical formula 2 is represented by any one of chemical formula 2-1 to chemical formula 2-6:
[ chemical formula 2-1]
Figure FDA0003722255800000032
[ chemical formula 2-2]
Figure FDA0003722255800000033
[ chemical formulas 2-3]
Figure FDA0003722255800000041
[ chemical formulas 2-4]
Figure FDA0003722255800000042
[ chemical formulas 2 to 5]
Figure FDA0003722255800000043
[ chemical formulas 2-6]
Figure FDA0003722255800000044
11. The photosensitive resin composition according to claim 7, wherein the shell represented by chemical formula 3 is represented by chemical formula 3-1:
[ chemical formula 3-1]
Figure FDA0003722255800000051
Wherein, in chemical formula 3-1,
R 11 is a hydrogen atom, a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group OR-C (= O) OR 16 Wherein R is 16 Is a substituted or unsubstituted C1 to C20 alkyl group,
R 12 to R 15 Each independently is a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group, and n is an integer of 1 to 3.
12. The photosensitive resin composition according to claim 7, wherein
The shell represented by chemical formula 3 is represented by any one of chemical formulas 3-1-1 to 3-1-3:
[ chemical formula 3-1-1]
Figure FDA0003722255800000061
[ chemical formula 3-1-2]
Figure FDA0003722255800000071
[ chemical formulas 3-1-3]
Figure FDA0003722255800000081
Wherein, in chemical formulas 3-1-1 to 3-1-3,
R 12 to R 15 Each independently a hydrogen atom,A halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
R 17 and R 18 Each independently a halogen atom, a substituted OR unsubstituted C1 to C20 alkyl group, OR-C (= O) OR 16 Wherein R is 16 Is a substituted or unsubstituted C1 to C20 alkyl group.
13. The photosensitive resin composition according to claim 7, wherein
The shell represented by chemical formula 3 has a cage width of 6.5 to 7.5 angstroms.
14. The photosensitive resin composition according to claim 7, wherein
The shell represented by chemical formula 3 is represented by any one of chemical formulae 3-a to 3-E:
[ chemical formula 3-A ]
Figure FDA0003722255800000091
[ chemical formula 3-B ]
Figure FDA0003722255800000101
[ chemical formula 3-C ]
Figure FDA0003722255800000111
[ chemical formula 3-D ]
Figure FDA0003722255800000121
[ chemical formula 3-E ]
Figure FDA0003722255800000131
15. The photosensitive resin composition according to claim 1, wherein
The core-shell structured dye comprises a core and a shell in a molar ratio of 1.
16. The photosensitive resin composition according to claim 1, wherein
The phthalocyanine-based dye is represented by chemical formula 4:
[ chemical formula 4]
Figure FDA0003722255800000141
Wherein, in chemical formula 4,
R 101 to R 116 Each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C6 to C20 aryloxy group,
provided that R 101 To R 104 At least one of R 105 To R 108 And R 109 To R 112 Are each independently represented by chemical formula 5, and
R 113 to R 116 Is a halogen atom or is represented by chemical formula 5,
[ chemical formula 5]
Figure FDA0003722255800000142
Wherein, in chemical formula 5,
R 117 and R 118 Each independently a halogen atom, a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl groupA base of
n1 and n2 are each independently an integer of 0 to 5, with the proviso that 1. Ltoreq. N1+ n 2. Ltoreq.5.
17. The photosensitive resin composition according to claim 16, wherein
Chemical formula 5 is represented by chemical formula 5-1 to chemical formula 5-4:
[ chemical formula 5-1]
Figure FDA0003722255800000151
[ chemical formula 5-2]
Figure FDA0003722255800000152
[ chemical formulas 5-3]
Figure FDA0003722255800000153
[ chemical formulas 5-4]
Figure FDA0003722255800000154
18. The photosensitive resin composition according to claim 1, wherein
The colorant further comprises a pigment.
19. The photosensitive resin composition according to claim 1, wherein
The colorant is contained in an amount of 1 to 15% by weight based on the total amount of the photosensitive resin composition.
20. The photosensitive resin composition according to claim 1, wherein
The photosensitive resin composition further comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
21. The photosensitive resin composition according to claim 20, wherein
Based on the total amount of the photosensitive resin composition,
the photosensitive resin composition comprises:
1 to 15 weight percent of the colorant;
1 to 20% by weight of the binder resin;
1 to 20% by weight of the photopolymerizable monomer;
0.1 to 10% by weight of the photopolymerization initiator; and
the remainder of the solvent.
22. The photosensitive resin composition according to claim 20, wherein
The photosensitive resin composition further includes malonic acid, 3-amino-1, 2-propanediol, a silane-based coupling agent having a vinyl group or a (meth) acryloyloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
23. A photosensitive resin layer produced using the photosensitive resin composition as described in any one of claims 1 to 22.
24. A color filter comprising the photosensitive resin layer of claim 23.
25. An electronic device comprising the color filter according to claim 24.
CN202210755246.4A 2021-07-02 2022-06-30 Photosensitive resin composition, photosensitive resin layer using same, color filter, and electronic device Pending CN115629522A (en)

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