CN109803960B - Compound, photosensitive resin composition containing the same and color filter - Google Patents
Compound, photosensitive resin composition containing the same and color filter Download PDFInfo
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- CN109803960B CN109803960B CN201780061147.3A CN201780061147A CN109803960B CN 109803960 B CN109803960 B CN 109803960B CN 201780061147 A CN201780061147 A CN 201780061147A CN 109803960 B CN109803960 B CN 109803960B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/66—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/36—Nitrogen atoms
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- Optical Filters (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention provides a compound comprising a cation and an anion, wherein the cation is represented by chemical formula 1, a photosensitive resin composition comprising the compound, and a color filter manufactured using the photosensitive resin composition. The compound according to the embodiment has improved heat resistance and light resistance, and the photosensitive resin composition including the compound can provide a color filter having improved brightness and durability. In chemical formula 1, each substituent is the same as defined in the specification. [ chemical formula 1]
Description
Technical Field
The present invention relates to a novel compound, a photosensitive resin composition comprising the same, and a color filter.
Background
Much research has been conducted on the preparation of pigments having uniform-sized particles, which can be prepared by treating the pigments after synthesis through manufacturing such as salt milling (salt milling) to facilitate stable dispersion state and refinement of pigment dispersion liquid. In addition, since the pigment has a limitation in brightness and contrast due to particle size (particle size), a color image sensor for an image sensor requires a much smaller dispersed particle size (particle diameter). Research into improving brightness, contrast, etc. is being conducted by not using pigments alone but using a mixture with dyes as a mixed colorant.
However, it has not been reported so far that the mixed colorant exhibits an excellent effect of improving properties such as heat resistance and brightness, compared to conventional colorants.
Therefore, it is necessary to study a suitable compound for use as a colorant in a photosensitive resin composition.
Disclosure of Invention
Technical problem
The embodiments of the present invention provide a novel compound.
Another embodiment provides a photosensitive resin composition comprising the compound.
Still another embodiment provides a color filter manufactured using the photosensitive resin composition.
Technical solution
The embodiment of the present invention provides a compound comprising a cation and an anion, wherein the cation is represented by chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the first and second,
R 1 to R 4 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 1 And R 2 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 3 And R 4 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 5 and R 6 Independently is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, with the proviso that R 5 And R 6 One of which is necessarily a substituted C3 to C20 alkyl group,
R 7 is a substituted or unsubstituted C6 to C20 aryl group, and
x is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group).
X can be O or S.
R 1 And R 2 And R 3 And R 4 One of which may be necessarily a substituted or unsubstituted C5 to C20 cycloalkyl.
R 5 And R 6 One of these may be necessarily a C3 to C20 alkyl group substituted with a 'C1 to C10 alkyl group, a C3 to C12 cycloalkyl group, or a C6 to C12 aryl group'.
The cation may be represented by one of chemical formulas 1-1 to 1-3.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
(A: adamantyl (Adamantanyl))
In chemical formulas 1-1 to 1-3,
R 1 and R 4 Independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R 5 and R 7 Independently a substituted or unsubstituted C6 to C20 aryl group,
R a 、R b 、R c 、R d and R 9 To R 11 Independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group, with the proviso that R 9 To R 11 Is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C12 aryl group, and
x is O or S.
The cation may be represented by one of chemical formulas 1a to 3 a.
[ chemical formula 1a ]
[ chemical formula 2a ]
[ chemical formula 3a ]
(A: adamantyl)
In chemical formulas 1a to 3a,
R 1 and R 4 Independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R a to R d Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R e to R h Independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R e and R f At least one of which is a halogen atom,
R g and R h Is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C12 aryl group,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group, and X is O or S.
The cation may be represented by one of chemical formulas 1-1a to 1-3 a.
[ chemical formula 1-1a ]
[ chemical formulas 1-2a ]
[ chemical formulas 1-3a ]
(A: adamantyl (Adamantanyl))
In chemical formulas 1-1a to 1-3a,
R 1 and R 4 Independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R a to R d Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R e and R f Independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R e and R f At least one of which is a halogen atom,
R g is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group, and
x is O or S.
The cation may be represented by one of chemical formulas 1-1 a-I to 1-3 a-I.
[ chemical formula 1-1 a-I ]
[ chemical formula 1-2 a-I ]
[ chemical formulas 1-3 a-I ]
(A: adamantyl (Adamantanyl))
In chemical formulae 1-1 a-I to 1-3 a-I,
R a to R d Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R e is a halogen atom, and is a halogen atom,
R g is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group,
x is O or S, and
R i to R l Independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.
R e May be, for example, a fluorine group (F) or a chlorine group (Cl).
The compound may be represented by one of chemical formulas 1-i to 1-v.
[ chemical formula 1-i ]
[ chemical formula 1-ii ]
[ chemical formulas 1-iii ]
[ chemical formulas 1-iv ]
[ chemical formula 1-v ]
In chemical formulas 1-i to 1-v,
Y - is anionic, and
x is O or S.
The anion may be represented by one selected from chemical formulas a to F.
[ chemical formula A ]
[ chemical formula B ]
[ chemical formula C ]
PW 12 O 40 3-
[ chemical formula D ]
SiW 12 O 40 4-
[ chemical formula E ]
CF 3 SO 3 -
[ chemical formula F ]
ClO 4 -
The compound including the cation and anion represented by chemical formula 1 may have a maximum transmittance (T) in a wavelength range of 400nm (nanometers) to 500nm max )。
Another embodiment provides a compound represented by chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R 21 to R 24 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 21 And R 22 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 23 And R 24 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 25 and R 26 Independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L 1 is a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, an ester linkage, a urethane linkage, or a combination thereof,
x is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group), and
Y - is an anion.
L 1 May be a substituted or unsubstituted C1 to C20 alkylene group, a divalent linking group represented by the formula L-1, or a divalent linking group represented by the formula L-2.
[ chemical formula L-1]
[ chemical formula L-2]
In the chemical formula L-1 and the chemical formula L-2,
L a to L g Independently a substituted or unsubstituted C1 to C10 alkylene.
R 21 And R 22 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 23 And R 24 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group may be cyclopentyl or cyclohexyl.
R 21 And R 22 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 23 And R 24 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group substituted with a halogen atom may be represented by formula S.
[ chemical formula S ]
R 25 May be a C6 to C20 aryl group substituted with F or Cl, and R 26 May be a C6 to C20 aryl group substituted with a C1 to C10 alkyl group.
The compound represented by chemical formula 2 may be represented by one of chemical formulae 2-i to 2-vi.
[ chemical formula 2-i ]
[ chemical formula 2-ii ]
[ chemical formula 2-iii ]
[ chemical formula 2-iv ]
[ chemical formula 2-v ]
[ chemical formula 2-vi ]
In chemical formulas 2-i to 2-vi,
x is O or S, and X is O or S,
L 2 is a substituted or unsubstituted C1 to C10 alkylene group, and
Y - is an anion.
Y - May be represented by one selected from chemical formulas a to F.
The compound represented by chemical formula 2 may have a maximum transmittance (T) in a wavelength range of 400nm to 500nm max )。
Another embodiment provides a compound represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the reaction mixture is,
R 31 to R 34 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstitutedSubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C20 heteroaryl, with the proviso that R 31 And R 32 Is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 33 And R 34 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 35 and R 36 Independently is a substituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and
L 3 is a C6 to C20 aromatic trivalent linker, a C3 to C20 heteroaromatic trivalent linker or a trivalent linker represented by the formula L-3,
[ chemical formula L-3]
(in the chemical formula L-3,
L 4 is a substituted or unsubstituted C1 to C10 alkylene group)
X is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), and
Y - is an anion.
L 3 May be a C3 to C10 nitrogen-containing heteroaromatic trivalent linker or a trivalent linker represented by the formula L-3.
The C3 to C10 nitrogen-containing heteroaromatic trivalent linker may be represented by the chemical formula L-4.
[ chemical formula L-4]
R 31 And R 32 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 33 And R 34 One of them can beIs a substituted or unsubstituted C3 to C20 cycloalkyl and the other may be a substituted or unsubstituted C6 to C20 aryl.
The C3 to C20 cycloalkyl group may be a cyclopentyl group or a cyclohexyl group.
R 31 And R 32 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 33 And R 34 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group substituted with a halogen atom may be represented by formula S.
[ chemical formula S ]
R 35 May be a C6 to C20 aryl group substituted with F or Cl, and R 36 May be a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group.
The compound represented by chemical formula 3 may be represented by one of chemical formulas 3-i to 3-v.
[ chemical formula 3-i ]
[ chemical formula 3-ii ]
[ chemical formula 3-iii ]
[ chemical formula 3-iv ]
[ chemical formula 3-v ]
In chemical formulas 3-i to 3-v,
x is O or S, and
Y - is an anion.
Y - May be represented by one selected from chemical formulas a to F.
The compound represented by the above chemical formula 3 may have a maximum transmittance (T) in a wavelength range of 400nm to 500nm max )。
Another embodiment provides a photosensitive resin composition comprising the compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.
The photosensitive resin composition may further comprise a pigment.
Still another embodiment provides a color filter manufactured using the photosensitive resin composition.
Other embodiments of the present invention are included in the detailed description below.
Effect of the invention
The compound according to the embodiment has improved heat resistance and light resistance, and the photosensitive resin composition including the compound can provide a color filter having improved brightness and durability.
Drawings
Is free of
Detailed Description
Hereinafter, examples of the present invention are explained in detail. However, these embodiments are exemplary, the invention is not limited thereto, and the invention is defined by the scope of the claims.
As used herein, the terms "substituted" and "substituted" when a specific definition is not otherwise provided refer to being selected from at least one ofSubstituent replacement: halogen (F, br, cl or I), hydroxy, nitro, cyano, amino (NH) 2 、NH(R 200 ) Or N (R) 201 )(R 202 ) Wherein R is 200 、R 201 And R 202 Is the same or different and is independently C1 to C10 alkyl), amidino, hydrazine, hydrazone, carboxyl, C1 to C20 alkyl, C1 to C20 alkenyl, C1 to C20 alkynyl, C3 to C20 alicyclic organic group, C6 to C20 aryl, and C2 to C20 heterocyclic group.
As used herein, when a specific definition is not otherwise provided, the term "alkyl group" refers to a C1 to C20 alkyl group and specifically a C1 to C15 alkyl group, the term "cycloalkyl group" refers to a C3 to C20 cycloalkyl group and specifically a C3 to C18 cycloalkyl group, the term "alkoxy group" refers to a C1 to C20 alkoxy group and specifically a C1 to C18 alkoxy group, the term "aryl group" refers to a C6 to C20 aryl group and specifically a C6 to C18 aryl group, the term "alkenyl group" refers to a C2 to C20 alkenyl group and specifically a C2 to C18 alkenyl group, the term "alkylene group" refers to a C1 to C20 alkylene group and specifically a C1 to C18 alkylene group, and the term "arylene group" refers to a C6 to C20 arylene group and specifically a C6 to C16 arylene group.
As used herein, "(meth) acrylate" means "acrylate" and "methacrylate" and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid" when a specific definition is not otherwise provided. As used herein, the term "combination" refers to mixing or copolymerization when a definition is not otherwise provided. In addition, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymer to random copolymer.
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, the hydrogen bonds at the position.
In the present specification, the cardogenous resin refers to a resin containing at least one functional group selected from the group consisting of chemical formulas 100-1 to 100-11 in a backbone (backbone).
As used herein, "a" indicates a point of attachment of the same or different atom or chemical formula when a specific definition is not otherwise provided.
The embodiment of the present invention provides a compound comprising a cation and an anion, wherein the cation is represented by chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the reaction mixture is,
R 1 to R 4 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R 1 and R 2 And R 3 And R 4 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 5 and R 6 Independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
R 5 and R 6 One of which is necessarily a substituted C3 to C20 alkyl group,
R 7 is a substituted or unsubstituted C6 to C20 aryl group, and
x is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group).
Recently, triarylmethane compounds, which are blue dyes for color filters having high brightness and high contrast, have been actively studied. The triarylmethane dye has high brightness in a wavelength range of 420nm to 450nm, but is not excellent in durability such as heat resistance, light resistance, etc., and has a limitation in use of a colorant in a color filter.
However, the compound including the cation represented by chemical formula 1 and the anion at R according to the embodiment 1 And R 2 And R 3 And R 4 Must contain a substituted or unsubstituted C3 to C20 cycloalkyl group at one position and thus can improve heat resistance, and also at R 5 And R 6 One of them must include a substituted C3 to C20 alkyl group and thus light resistance can be improved, and thus, when a compound including a cation and an anion represented by chemical formula 1 is used, a color filter having excellent durability such as heat resistance, light resistance, and the like, as well as high brightness and high contrast can be provided.
In addition, a compound represented by chemical formula 2, which will be described later, is represented at R 21 And R 22 And R 23 And R 24 Must contain a substituted or unsubstituted C3 to C20 cycloalkyl group at one position and thus can improve heat resistance, and also at R 25 And R 26 Contains a substituted C1 to C20 alkyl group (e.g., a substituted C3 to C20 alkyl group) at least one of them and thus can improve light resistance, and thus, a color filter having excellent durability such as heat resistance, light resistance, and high brightness and high contrast can be provided by using the compound represented by chemical formula 2.
In addition, a compound represented by chemical formula 3, which will be described later, is represented at R 31 And R 32 And R 33 And R 34 Must include a substituted or unsubstituted C3 to C20 cycloalkyl group at one position and thus can improve heat resistance, and also at R 35 And R 36 Includes a substituted C1 to C20 alkyl group (e.g., a substituted C3 to C20 alkyl group) and thus light resistance can be improved, and thus, a color filter having excellent durability such as heat resistance, light resistance, and high brightness and high contrast can be provided by using the compound represented by chemical formula 3.
For example, X may be O or S.
For example, R 1 And R 2 And R 3 And R 4 One of which may be necessarily a substituted or unsubstituted C5 to C20 cycloalkyl group, and in particular a substituted or unsubstituted C5 to C12 cycloalkyl group, for example a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted adamantyl group.
Adamantyl can be represented by the formula Ad.
[ chemical formula Ad ]
R 5 And R 6 One of them may be necessarily a C3 to C20 alkyl group substituted with a C1 to C10 alkyl group, a C3 to C12 cycloalkyl group, or a C6 to C12 aryl group, and specifically a C3 to C20 alkyl group substituted with a C1 to C4 alkyl group such as a secondary carbon (e.g., isopropyl group) or a tertiary carbon (e.g., tert-butyl group).
The cation may be specifically represented by one of chemical formulas 1-1 to 1-3.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
(A: adamantyl)
In chemical formulas 1-1 to 1-3,
R 1 and R 4 Independently is substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstitutedA substituted C6 to C20 aryl or a substituted or unsubstituted C2 to C20 heteroaryl,
R 5 and R 7 Independently a substituted or unsubstituted C6 to C20 aryl group,
R a 、R b 、R c 、R d and R 9 To R 11 Independently hydrogen, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C12 aryl,
x is O or S, and
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C12 aryl group.
R 9 To R 11 At least two of which may be substituted or unsubstituted C1 to C10 alkyl.
The cation may be more specifically represented by one of chemical formulas 1a to 3 a.
[ chemical formula 1a ]
[ chemical formula 2a ]
[ chemical formula 3a ]
(A: adamantyl)
In chemical formulas 1a to 3a,
R 1 and R 4 Independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group,
R a to R d Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,
R e to R h Independently hydrogen, halogen or substituted or unsubstituted C1 to C20 alkyl,
R e and R f At least one of which is a halogen,
R g and R h Is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently hydrogen, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C12 aryl,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group, and
x is O or S.
In addition, the cation may be represented by one of chemical formulas 1-1a to 1-3a, for example.
[ chemical formula 1-1a ]
[ chemical formulas 1-2a ]
[ chemical formulas 1-3a ]
(A: adamantyl (Adamantanyl))
In chemical formulas 1-1a to 1-3a,
R 1 and R 4 Independently is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstitutedA substituted C2 to C20 heteroaryl group,
R a to R d Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,
R e and R f Independently hydrogen, halogen or substituted or unsubstituted C1 to C20 alkyl,
R e and R f At least one of which is a halogen,
R g is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group, and
x is O or S.
In particular, R e And R f At least one of which may be present at ortho (ortho) or meta (meta), specifically ortho (ortho), and more specifically represented by one of chemical formulae 1-1 a-i to 1-3 a-i.
[ chemical formula 1-1 a-I ]
[ chemical formula 1-2 a-I ]
[ chemical formulas 1-3 a-I ]
(A: adamantyl)
In chemical formulae 1-1 a-I to 1-3 a-I,
R a to R d Independently hydrogen or substituted or unsubstitutedA C1 to C10 alkyl group of (a),
R e is a halogen, and the halogen is a halogen,
R g is a substituted or unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently hydrogen or substituted or unsubstituted C1 to C10 alkyl,
R 9 to R 11 Is a substituted or unsubstituted C1 to C10 alkyl group,
x is O or S, and the compound is shown in the specification,
R i to R l Independently hydrogen, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 aryl, or substituted or unsubstituted C2 to C20 heteroaryl, specifically hydrogen, halogen, or substituted or unsubstituted C1 to C20 alkyl, and more specifically hydrogen, fluoro, chloro, or substituted or unsubstituted C1 to C10 alkyl.
R e May be, for example, fluorine or chlorine.
For example, the compound may be represented by one of chemical formulas 1-i to 1-v, but is not limited thereto.
[ chemical formula 1-i ]
[ chemical formula 1-ii ]
[ chemical formulas 1-iii ]
[ chemical formulas 1-iv ]
[ chemical formula 1-v ]
In chemical formulas 1-i to 1-v,
Y - is an anion of the anion-forming polymer,
x is O or S.
From Y - The anion represented may be selected from formula a to formula F, but is not limited thereto.
[ chemical formula A ]
[ chemical formula B ]
[ chemical formula C ]
PW 12 O 40 3-
[ chemical formula D ]
SiW 12 O 40 4-
[ chemical formula E ]
CF 3 SO 3 -
[ chemical formula F ]
ClO 4 -
Another embodiment provides a compound represented by chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R 21 to R 24 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 21 And R 22 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group, and R 23 And R 24 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 25 and R 26 Independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group,
L 1 is a substituted or unsubstituted C1 to C10 alkylene, a substituted or unsubstituted C3 to C20 cycloalkylene, an ester linkage, a urethane linkage, or a combination thereof,
x is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), and
Y - is an anion.
L 1 May be a substituted or unsubstituted C1 to C20 alkylene group, a divalent linking group represented by the formula L-1 or a divalent linking group represented by the formula L-2.
[ chemical formula L-1]
[ chemical formula L-2]
In the chemical formula L-1 and the chemical formula L-2,
L a to L g Independently a substituted or unsubstituted C1 to C10 alkylene.
R 21 And R 22 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl groupAnd the other may be a substituted or unsubstituted C6 to C20 aryl, and R 23 And R 24 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group may be a cyclopentyl group or a cyclohexyl group.
R 21 And R 22 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 23 And R 24 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group substituted with a halogen atom may be represented by formula S.
[ chemical formula S ]
R 25 May be C6 to C20 aryl substituted with F or Cl and R 26 May be a C6 to C20 aryl group substituted with a C1 to C10 alkyl group.
For example, R 26 May be a C3 to C20 alkyl group substituted with a C1 to C4 alkyl group such as a secondary carbon (e.g., isopropyl) or a tertiary carbon (e.g., tert-butyl).
The compound represented by chemical formula 2 may be represented by one of chemical formulas 2-i to 2-vi, but is not limited thereto.
[ chemical formula 2-i ]
[ chemical formula 2-ii ]
[ chemical formula 2-iii ]
[ chemical formula 2-iv ]
[ chemical formula 2-v ]
[ chemical formula 2-vi ]
In chemical formulas 2-i to 2-vi,
x is O or S, and X is O or S,
L 2 is a substituted or unsubstituted C1 to C10 alkylene group, and
Y - is an anion.
Y - May be represented by one selected from chemical formulas a to F, but is not limited thereto.
Another embodiment provides a compound represented by chemical formula 3.
[ chemical formula 3]
In the chemical formula 3, the reaction mixture is,
R 31 to R 34 Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 31 And R 32 One of which must be substituted orUnsubstituted C3 to C20 cycloalkyl, and R 33 And R 34 One of which is necessarily a substituted or unsubstituted C3 to C20 cycloalkyl group,
R 35 and R 36 Independently is a substituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and
L 3 is a C6 to C20 aromatic trivalent linker, a C3 to C20 heteroaromatic trivalent linker or a trivalent linker represented by the chemical formula L-3,
[ chemical formula L-3]
(in the chemical formula L-3,
L 4 is a substituted or unsubstituted C1 to C10 alkylene group)
X is O, S or NR 8 (R 8 Is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group), and
Y - is an anion.
L 3 May be a C3 to C10 nitrogen-containing heteroaromatic trivalent linker or a trivalent linker represented by the formula L-3.
The C3 to C10 nitrogen-containing heteroaromatic trivalent linking group may be represented by the chemical formula L-4.
[ chemical formula L-4]
R 31 And R 32 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 33 And R 34 One of which may be a substituted or unsubstituted C3 to C20 cycloalkyl group and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group may be a cyclopentyl group or a cyclohexyl group.
R 31 And R 32 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group, and R 33 And R 34 One of which may be a C3 to C20 cycloalkyl group substituted with a halogen atom and the other may be a substituted or unsubstituted C6 to C20 aryl group.
The C3 to C20 cycloalkyl group substituted with a halogen atom may be represented by formula S.
[ chemical formula S ]
R 35 May be C6 to C20 aryl substituted with F or Cl and R 36 May be a C1 to C20 alkyl group substituted with a C1 to C10 alkyl group.
R 35 May be a C6 to C20 aryl group substituted by F or C-and R 36 May be a C6 to C20 aryl group substituted with a C1 to C10 alkyl group.
For example, R 36 May be a C3 to C20 alkyl group substituted with a C1 to C4 alkyl group such as a secondary carbon (e.g., isopropyl) or a tertiary carbon (e.g., t-butyl).
The compound represented by chemical formula 3 may be represented by one of chemical formulas 3-i to 3-v, but is not limited thereto.
[ chemical formula 3-i ]
[ chemical formula 3-ii ]
[ chemical formula 3-iii ]
[ chemical formula 3-iv ]
[ chemical formula 3-v ]
In chemical formulas 3-i to 3-v,
x is O or S, and
Y - is an anion.
Y - May be represented by one selected from the group consisting of chemical formulas a to F, but is not limited thereto.
The compound according to the embodiment includes a cation and an anion represented by chemical formula 1, or is represented by chemical formula 2 or chemical formula 3, and thus when used as a colorant, may provide a display device having excellent color characteristics such as brightness, contrast, and the like. For example, the compound may be a colorant, such as a dye, such as a blue dye, such as having a maximum absorbance (λ) at a wavelength in the range of from 600nm to 700nm, such as from 610nm to 680nm, such as from 610nm to 650nm max ) The dye of (4). For example, the compound may be of T at a wavelength in the range 400nm to 450nm, such as 420nm to 450nm, such as 430nm to 450nm max The dye of (4). T is max Refers to the maximum transmittance.
In general, dyes are the most expensive of the components used in color filters. Thus, it may be necessary to use more expensive dyes to achieve the desired effect (e.g., high brightness, high contrast, etc.) and thus increase the unit production cost. However, when the compounds according to the examples are used as dyes in a color filter, the compounds can achieve excellent color characteristics such as high brightness, high contrast, etc. and reduce unit production costs even when used in a small amount.
According to another embodiment, a photosensitive resin composition includes the compound according to the embodiment (a compound including a cation and an anion represented by chemical formula 1, a compound represented by chemical formula 2, and/or a compound represented by chemical formula 3).
For example, the photosensitive resin composition may include the compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
For example, the photosensitive resin composition may further include a pigment.
The compounds according to the embodiments function as a colorant (e.g., a dye such as a blue dye) in the photosensitive resin composition and can achieve excellent color characteristics.
The compound according to the embodiment may be included in an amount of 1 to 10 wt%, specifically 1 to 8 wt%, and more specifically 1 to 5 wt%, for example 3 to 5 wt%, based on the total amount of the photosensitive resin composition. When the compound according to the embodiment is included in the range, color reproducibility and contrast are improved.
The pigment may include, but is not limited to, a blue pigment, a yellow pigment, a green pigment, a red pigment, a violet pigment, or a combination thereof.
For example, the pigment may be contained in the photosensitive resin composition in the form of a pigment dispersion.
The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment in the solvent.
The solid pigment may be included in an amount of 1 to 20 wt%, such as 8 to 20 wt%, for example 15 to 20 wt%, such as 8 to 15 wt%, for example 10 to 20 wt%, for example 10 to 15 wt%, based on the total amount of the pigment dispersion.
The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like. Specific examples of the dispersant may be polyalkylene glycol and esters thereof, polyoxyalkylene, polyol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide addition products, alkylamines, and the like, and may be used alone or in a mixture of two or more.
Commercially available examples of dispersants may include DISPERBYK (DISPERBYK) -101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like, made by ByK Co., ltd.; EFKA 47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, and the like, which are manufactured by EFKA Chemicals co; solsperse (soxpa) 5000, solsperse 12000, solsperse 13240, solsperse 13940, solsperse 17000, solsperse 20000, solsperse 24000GR, solsperse 27000, solsperse 28000, and the like, manufactured by zenika co., inc (Zeneka co.); or PB711 or PB821 manufactured by Ajinomoto inc.
The dispersant may be included in an amount of 1 to 20% by weight, based on the total amount of the pigment dispersion liquid. When the dispersant is included within the range, the dispersion of the photosensitive resin composition is improved due to appropriate viscosity, and thus optical quality, physical quality, and chemical quality can be maintained when the photosensitive resin composition is applied to a product.
The solvent used for forming the pigment dispersion liquid may be ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or the like.
The pigment dispersion may be contained in an amount of 5 to 30% by weight, for example, 10 to 25% by weight, based on the total amount of the photosensitive resin composition. When the pigment dispersion is included within the range, a manufacturing margin may be secured and color reproducibility and contrast may be improved.
The binder resin may be an acrylic binder resin, a cardo-poly binder resin, or a combination thereof.
The acrylic binder resin is 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.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group. Examples of the monomer include (meth) acrylic 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 acrylic resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, alpha-methylstyrene, vinyltoluene, vinylbenzyl methyl ether, or the like; 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, phenyl (meth) acrylate, and the like; unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and the like; vinyl carboxylate compounds such as vinyl acetate, vinyl benzoate and the like; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate and the like; vinyl cyanide compounds such as (meth) acrylonitrile and the like; unsaturated amide compounds such as (meth) acrylamide and the like; and the like, and may be used alone or in a mixture of two or more.
Specific examples of the acrylic binder resin may be a poly (benzyl methacrylate) copolymer, a (meth) acrylic acid/benzyl methacrylate/styrene copolymer, a (meth) acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, a (meth) acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto. These acrylic binder resins may be used alone or in a mixture of two or more.
The weight average molecular weight of the acrylic binder resin can be 3,000g/mol to 150,000g/mol, such as 5,000g/mol to 50,000g/mol, such as 20,000g/mol to 30,000g/mol. When the weight average molecular weight of the acrylic binder resin is within the range, the photosensitive resin composition has good physical and chemical properties, an appropriate viscosity, and close contact properties with a substrate during color filter manufacturing.
The acid value of the acrylic adhesive resin may be 15mgKOH/g (milliKOH/g) to 60mgKOH/g, for example, 20mgKOH/g to 50mgKOH/g. When the acid value of the acrylic binder resin is within the range, the pixel pattern may have excellent resolution.
The cardmultisystem adhesive resin may include a repeating unit represented by chemical formula 100.
[ chemical formula 100]
In the chemical formula 100, the chemical formula is shown,
R 101 and R 102 Independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R 103 and R 104 Independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and
Z 1 is a single bond, O, CO, SO 2 、CR 15 R 16 、SiR 17 R 18 (wherein, R 15 To R 18 Independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by chemical formula 100-1 to chemical formula 100-11,
[ chemical formula 100-1]
[ chemical formula 100-2]
[ chemical formula 100-3]
[ chemical formula 100-4]
[ chemical formula 100-5]
(wherein, in the chemical formula 100-5,
R x is a hydrogen atom, an ethyl group, C 2 H 4 Cl、C 2 H 4 OH、CH 2 CH＝CH 2 Or a phenyl group. )
[ chemical formulas 100-6]
[ chemical formulas 100-7]
[ chemical formulas 100-8]
[ chemical formulas 100-9]
[ chemical formulas 100-10]
[ chemical formulas 100-11]
Z 2 Is a residue of an acid dianhydride, and
m1 and m2 are independently integers ranging from 0 to 4.
The carden multisystem adhesive resin may include a functional group represented by chemical formula 101 at least one of both ends.
[ chemical formula 101]
In the chemical formula 101, the chemical formula is shown,
Z 3 may be represented by chemical formula 101-1 to chemical formula 101-7.
[ chemical formula 101-1]
(in chemical formula 101-1, R w And R y Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group. )
[ chemical formula 101-2]
[ chemical formula 101-3]
[ chemical formula 101-4]
[ chemical formula 101-5]
(in chemical formula 101-5, R z Is O, S, NH, substituted or unsubstituted C1 to C20 alkylene, C1 to C20 alkylamino or C2 to C20 alkenylamino. )
[ chemical formulas 101-6]
[ chemical formulas 101-7]
Cardol resins can be prepared, for example, by mixing at least two of the following compounds: fluorene-containing compounds such as 9, 9-bis (4-oxacyclopropylmethoxyphenyl) fluorene and the like; acid anhydride compounds such as pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, tetrahydrophthalic anhydride, and the like; glycol compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and the like; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, benzyl alcohol and the like; solvent-based compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine, etc.; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.
When the carden multi-component binder resin is used together with the acrylic binder resin, a photosensitive resin composition having excellent close contact force, high resolution and high brightness characteristics can be obtained.
The weight average molecular weight of the cardo multi-component binder resin may be in the range of 500g/mol to 50,000g/mol, for example 3,000g/mol to 30,000g/mol. When the weight average molecular weight of the carden multisystem binder resin is within the range, a satisfactory pattern can be formed without residue during the manufacture of the color filter and without reducing the film thickness during development.
The cardo binder resin may have an acid value of from about 100mgKOH/g to about 140mgKOH/g.
The binder resin may be included in an amount of 1 to 30 wt%, for example, 1 to 15 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, developability may be improved, and excellent surface smoothness may be improved due to improved crosslinking during the manufacture of the color filter sheet.
The photopolymerizable compound may be a monofunctional ester or a polyfunctional ester of (meth) acrylic acid containing at least one ethylenically unsaturated double bond.
The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during exposure in pattern formation fabrication and form a pattern having excellent heat resistance, light resistance, and chemical resistance.
Specific examples of the photopolymerizable compound 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 compounds are as follows. Examples of the monofunctional ester of (meth) acrylic acid may include Aronix (Oronix) of Toagosei Chemistry Industry Co., ltd., east Asia synthetic chemical Co., ltd.)
KAYARAD (KAYALADE) available from Nippon Kayaku Co., ltd>
Du/R of Osaka Organic Chemical industry Co., ltd>
And the like. Examples of the bifunctional ester of (meth) acrylic acid may include Rhones (Co.) of Toyo chemical Co., ltd>
KAYARAD (Kayaka) of Japan Chemicals Co., ltd>
Based on Osaka organic chemical Co., ltd>
V-335/>
And so on. Examples of the trifunctional ester of (meth) acrylic acid may include Aronia, manufactured by Toyo chemical Synthesis Co., ltd
KAYARAD (Kayaka) of Japan Chemicals Co., ltd>
Osaka Okauki Kayaku Kogyo Co. Ltd. (Co Ltd.). Ika organic chemical Co., ltd.))>
And the like. The photopolymerizable compounds may be used alone or in a mixture of two or more.
The photopolymerizable compound may be treated with an acid anhydride to improve developability.
The photopolymerizable compound may be included in an amount of 1 to 15 wt%, for example, 5 to 10 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the range, the photopolymerizable compound is sufficiently cured during exposure for pattern formation manufacture and has excellent reliability, and the developability of the alkaline developer can be improved.
The photopolymerization initiator is an initiator commonly used for photosensitive resin compositions, such as acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, or a combination thereof.
Examples of the acetophenone-based compound 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, benzoylmethyl benzoate, 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 the benzoin-based compound 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- (naphthol-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2-4-bis (trichloromethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6-methoxystyryl-s-triazine, and the like.
Examples of the oxime-based compound may be O-acyloxime-based compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione, 1- (O-acetyloxime) -1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone, O-ethoxycarbonyl- α -oxyamino-1-phenylpropan-1-one, and the like. Specific examples of the O-acyloxime-based compound may be 1, 2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 1- (4-phenylthiophenyl) -butane-1, 2-dione 2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -octane-1, 2-dione 2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -oct-1-ketoxime-O-acetate, 1- (4-phenylthiophenyl) -butan-1-ketoxime-O-acetate, and the like.
The photopolymerization initiator may further contain a carbazole-based compound, a diketone-based compound, a sulfonium borate-based compound, an azide-based compound, an imidazole-based compound, a bisimidazole-based compound, a fluorene-based compound, and the like, in addition to the above-mentioned compounds.
The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transmitting its energy.
Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.
The photopolymerization initiator may be included in an amount of 0.01 to 10% by weight, 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 range, excellent reliability may be secured due to sufficient curing during exposure in pattern formation manufacturing, a pattern may have excellent resolution and close contact properties as well as excellent heat resistance, light resistance, and chemical resistance, and transmittance may be prevented from being deteriorated due to a non-reactive initiator.
The solvent is a material having compatibility with, but not reacting with, the compound according to the example, the pigment, the binder resin, the photopolymerizable compound and the photopolymerization initiator.
Examples of the solvent may include 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 monomethyl ether, ethylene glycol monoethyl ether, and the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve 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.; lactates such as methyl lactate, ethyl lactate, and the like; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxopropionates such as methyl 3-oxopropionate, ethyl 3-oxopropionate, etc.; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionates such as methyl 2-oxopropionate, ethyl 2-oxopropionate, propyl 2-oxopropionate, etc.; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxo-2-methylpropionates such as methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate and the like; mono-oxo-monocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate and the like; ketoesters such as ethyl pyruvate, and the like, and further, high boiling point solvents such as N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidinone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, 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, phenylcellosolve acetate, and the like can also be used.
In view of miscibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether and the like; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate and the like; esters such as ethyl 2-hydroxypropionate and the like; carbitols 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 is used in an amount of 30 to 90 wt% as the balance, based on the total amount of the photosensitive resin composition. When the solvent is included in the range, the photosensitive resin composition may have an appropriate viscosity, thereby causing an improvement in coating characteristics of the color filter.
The photosensitive resin composition according to another embodiment may further include an epoxy compound to improve the close contact property with the substrate.
Examples of the epoxy compound may be a phenol novolac epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol a epoxy compound, an alicyclic epoxy compound, or a combination thereof.
The epoxy compound may be included in an amount of 0.01 to 20 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the range, the close contact property, the storage capacity, and the like can be improved.
The photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, etc. to improve adhesion with a substrate.
Examples of the silane coupling agent include trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and the like. These silane coupling agents may be used alone or in admixture of two or more.
The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is contained within the above range, the close contact property, the storage property, and the like are improved.
The photosensitive resin composition may further include a surfactant to improve coating properties and suppress the generation of spots.
Of surfactantsExamples may include fluorene-based surfactants such as those of BM chemical company (BM Chemie Inc.;)
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The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the range, coating uniformity may be ensured, stains are not generated, and wetting properties of the glass substrate are improved.
The photosensitive resin composition may further contain other additives such as an antioxidant, a stabilizer, etc., in a predetermined amount at the time of its property reduction.
According to another embodiment, there is provided a color filter manufactured using the photosensitive resin composition according to the embodiment.
Patterning of the color filter is made as follows.
The manufacturing method comprises coating a positive photosensitive resin composition on a supporting substrate by spin coating, slit coating, ink jet printing, etc.; drying the coated positive photosensitive resin composition to form a photosensitive resin composition film; exposing the positive photosensitive resin composition film; developing the exposed positive photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin film; and heat-treating the photosensitive resin film. Conditions for the patterning manufacturing are well known in the related art and will not be described in detail in this specification.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
(example of Synthesis)
Synthesis example 1: synthesis of Compound represented by the formula P-1
1. The first step is as follows: synthesis of intermediate 1
Reacting NaBH 4 (3.8 g (g), 0.1 mol) was placed in a round bottom flask, 100g of 1,2-dichloroethane (1, 2-dichloroethane) was added thereto, and the mixture was cooled to 0 ℃ and then stirred. Acetic acid (21.6 g, 0.36mol) was added thereto, the obtained mixture was stirred for 2 hours while slowly heating to room temperature, and cyclohexanone (8.8g, 0.09mol) was added dropwise thereto. The reaction was stirred at room temperature for 1 hour, aniline (aniline) (7.9 g, 0.85mol) was added thereto, and the resulting mixture was allowed to stand at room temperature overnight (overnight). When the reaction was completed, an extract was obtained using Dichloromethane (dichromethane), and then washing was performed using distilled water and 10% NaCl aqueous solution. In the presence of MgSO 4 After removing water therefrom, the extract was filtered and then dried to obtain intermediate 1 (14.5 g, yield 97%).
[ intermediate 1]
2. The second step is as follows: synthesis of intermediate 2
4,4'-dichlorobenzophenone (4, 4' -dichlorobenzophenone) (10g, 39.8mmol (mmol)), and Pd were reacted under a nitrogen atmosphere 2 (dba) 3 (tris (dibenzylideneacetone) dipalladium (0)) (220 mg (mg), 0.002 mol%), XPhos (2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl) (230mg, 0.005mol%) and sodium t-butoxide (sodium t-butoxide) (11.48g, 119.5 mmol) were placed in a round bottom flask, 50g of toluene (toluene) were added thereto, the mixture was stirred at room temperature for 10 minutes, and intermediate 1 (14g, 79.6 mmol) was added thereto. The reaction was stirred for 2 hours while heating slowly to 80 ℃. When the reaction was completed, the reaction was cooled to room temperature, 50g of isopropyl alcohol (isopropanol) was added thereto, and the obtained mixture was stirred. The sediment in the filter is filteredFiltration was performed, washing was performed with water, and then added to acetonitrile (acetonitrile), and the obtained mixture was stirred at 80 ℃ for 30 minutes. After the temperature was decreased to room temperature, the precipitate was filtered and dried to obtain intermediate 2 (27.3 g, yield 65%).
[ intermediate 2]
3. Third to sixth steps: synthesis of intermediate 3 to intermediate 6
[ reaction scheme 1]
(1) The third step: synthesis of intermediate 3
Sodium ethoxide (34.2 g, 0.503mol) and 250g ethanol (ethanol) were placed in a round bottom flask and stirred at room temperature for 30 minutes, to which ethyl cyanoacetate (45.5 g, 0.402mol) was slowly added, and the mixture was stirred at room temperature for 30 minutes. O-tolylisothiocyanate (O-tolylisothiocyanate) (50g, 0.335 mol) was slowly added dropwise thereto, and the obtained mixture was heated to 80 ℃ and then stirred for 3 hours. When the reaction was complete, the biomass was cooled, the solvent was removed therefrom, and an extract was obtained using dichloromethane (dichloromethane) and washed with 10% HCl and water, respectively. After removing the organic solvent therefrom, 200g of MeOH was added to the solid compound therein, and the obtained mixture was stirred at 0 ℃ for 30 minutes, and then filtered to obtain intermediate 3 (73.8 g, yield 84%).
[ intermediate 3]
1 H NMR (proton Nuclear magnetic resonance) (solvent: CDCl) 3 (deuterochloroform)): 11.5 (bs, 1H), 7.36-7.22 (m, 4H), 4.61 (s, 1H), 4.29 (q, 2H), 1.37 (t, 3H).
GC-MS (gas chromatography-mass spectrometry): 262m/z (mass-to-charge ratio).
(2) The fourth step: synthesis of intermediate 4
NaOH (45.7 g,1.1 mol) and 240 g of water were placed in a round bottom flask, the mixture was stirred at 0 ℃ for 30 minutes, intermediate 3 (30g, 0.114mol) was added thereto, and the mixture was heated to 80 ℃ and then stirred for 3 hours. When the reaction was complete, the temperature was lowered to 0 ℃ and the reaction was then acidified (acid) with concentrated (conc.) HCl (pH: about 6). The precipitate formed therein was filtered, and then washed with water and dried to obtain intermediate 4 (19.7 g, yield 90%).
[ intermediate 4]
1 H NMR (solvent): CDCl 3 )：9.24(bs,1H),7.43-7.28(m,4H),4.08(s,2H)。
GC-MS：190m/z。
(3) The fifth step: synthesis of intermediate 5
KOH (8.71g, 0.155mol) and 200g of MeOH were placed in a round-bottom flask, and then stirred at room temperature for 30 minutes, to which intermediate 4 (20.5 g, 0.108mol) and 2 '-chlorobenzoyl methyl bromide (2' -chlorophenylacyl bromide) (26.6 g, 0.114mol) were added, respectively, and the mixture was stirred at room temperature for 2 hours. When the reaction was completed, 200g of water was added thereto, the obtained mixture was stirred at room temperature for 1 hour, and the precipitate therein was filtered, and then washed with MeOH and dried to obtain intermediate 5 (29.8 g, yield 89%).
[ intermediate 5]
1 H NMR (solvent): CDCl 3 )：7.46-7.40(m,3H),7.33-7.24(m,4H),7.12(t,1H),6.64(bs,1H),6.46(s,1H),2.34(t,3H)。
GC-MS：324m/z。
(4) A sixth step: synthesis of intermediate 6
KOH (10.4 g, 0.185mol), 170g of acetone (acetone) and 80g of water were placed in a round-bottom flask, and then stirred at room temperature, to which intermediate 5 (30g, 92.4 mmol) and 2-iodopropane (2-iodopropane) (31.5 g, 0.185mol) were added, respectively, and the mixture was stirred at 60 ℃ for 12 hours. When the reaction was completed, acetone (acetone) was removed by distillation, an extract was obtained using dichloromethane (dichloromethane) and then washed using 10% HCl and saturated sodium thiosulfate (sat. After the organic solvent was removed therefrom, a precipitate was formed using Ethyl acetate/Hexane (Ethyl acetate/Hexane) to obtain intermediate 6 (19 g, 56% yield).
[ intermediate 6]
1 H NMR (solvent): CDCl 3 )：7.42-7.40(m,1H),7.34-7.20(m,7H),6.27(s,1H),4.72-4.63(m,1H),2.28(s,3H),1.28(d,6H)。
GC-MS：366m/z。
4. A seventh step of: synthesis of Compound represented by the formula P-1
Intermediate 2 (1.50g, 2.83mmol) and intermediate 6 (1.0g, 2.83mmol) were placed in a round-bottomed flask under nitrogen, and 7.5 g of toluene (toluene) and POCl were added thereto 3 (2.6g, 17.0 mmol), and the mixture was stirred for 5 hours while slowly heating to 110 ℃. When the reaction is complete, the temperature is increasedThe temperature was reduced to room temperature, and an extract was obtained using Methyl Ethyl Ketone (MEK) and washed with 10% NaCl, water, and 10% HCl, respectively. After removing the organic layer, the residue was dried and then added to Lithium bis (trifluoromethyl) sulfonimide (1.2 g,4.2 mmol), 10g of dimethyl sulfoxide (DMSO) was added thereto, and the obtained mixture was stirred at room temperature for 30 minutes (anion exchange manufacturing). The reactant was dropped (dropping) into water to form a precipitate, and the precipitate was filtered and separated. The filtered solid compound was dissolved in 40g of acetonitrile (acetonitrile), 3g of activated carbon was added thereto, and the obtained mixture was stirred for 30 minutes. The activated carbon was removed through a filter, and a filtrate obtained therefrom was removed by distillation and dried to obtain a compound represented by the formula P-1 (2.69 g, yield 82%).
[ chemical formula P-1]
1 H NMR (solvent): CDCl 3 )：7.54-7.34(m,10H),7.23-7.18(m,4H),7.09-7.03(m,8H),6.42(d,4H),4.69-4.50(m,1H),4.00(m,2H),2.31(s,3H),1.96-1.80(m,8H),1.68-1.36(m,8H),1.25-1.08(m,10H)。
LC-Mass (liquid chromatography-Mass Spectrometry): 877m/z (molecular weight of cation only detected when LC-Mass is in + mode).
Synthesis example 2: synthesis of Compound represented by the formula P-2
(1) Synthesis of intermediate 5-1
Intermediate 5-1 (16.1 g, 83% yield) was synthesized in the same manner as in the synthesis of intermediate 5, except that 2 '-fluorobenzoylmethyl bromide (2' -chlorophenylmethyl bromide) (14.4 g, 66mmol) was used instead of 2 '-chlorobenzoylmethyl bromide (2' -chlorophenylacyl bromide).
[ intermediate 5-1]
(2) Synthesis of intermediate 6-1
Intermediate 6-1 (13.2 g, yield 38% relative to intermediate 5-1) was synthesized according to the same method as intermediate 6, except that intermediate 5-1 (16.1g, 52mmol) and 1,6-Diiodohexane (1, 6-Diiodohexane) (8.5g, 25mmol) were used instead of intermediate 5 and 2-iodopropane (2-iodopropane).
[ intermediate 6-1]
(3) Synthesis of Compound represented by the formula P-2
Intermediate 2 (1.0 g, 1.89mmol) and intermediate 6-1 (0.66g, 0.94mmol) were placed in a round-bottomed flask under nitrogen, to which 5g of toluene (toluene) and POCl were added 3 (1.7g, 11.3mmol) and the mixture was stirred for 5 hours while heating slowly to 110 ℃. When the reaction was completed, the temperature was lowered to room temperature, and an extract was obtained using Methyl Ethyl Ketone (MEK) and washed using 10% NaCl, water, and 10% HCl, respectively. After removing the organic layer, the residue was dried, lithium bis (trifluoromethyl) sulfonimide (0.8g, 2.8mmol) was added thereto, 7g of dimethyl sulfoxide (DMSO) was added thereto, and the obtained mixture was stirred at room temperature for 30 minutes (anion exchange process). Next, the reactant was dropped (dropping) into water to form a precipitate, and the precipitate was separated by a filter. The obtained solid compound was added to 40g of acetonitrile (acetonitrile), 2g of activated carbon was added thereto, and the obtained mixture was stirred for 30 minutes. After the activated carbon was removed by a filter, the filtrate obtained therefrom was removed by distillation, and dried to obtain a compound represented by the formula P-2 (1.3 g,the yield was 61% with respect to intermediate 6-1).
[ chemical formula P-2]
1 H NMR (solvent): CDCl 3 )：7.50-7.03(m,44H),6.42(m,8H),4.13-3.99(m,6H),3.70(m,2H),2.30(s,6H),2.04-0.84(m,48H)。
LC-Mass (liquid chromatography-Mass Spectrometry): 861m/z (the actual molecular weight of the cation is 1722, but half of the actual molecular weight was detected since the cation was divalent).
Synthesis example 3: synthesis of Compound represented by the formula P-3
(1) Synthesis of intermediate 6-2
Intermediate 6-2 (15.1 g, yield 89%) was synthesized according to the same method as the synthesis of intermediate 6, except that 2-iodoethanol (2-iodoethanol) (10.3 g, 60mmol) was used instead of intermediate 5 (15g, 46mmol) and 2-iodopropane (2-iodopropane).
[ intermediate 6-2]
(2) Synthesis of intermediate 7
Cyanuric chloride (cyanic chloride) (0.36g, 1.9mmol) and 10mL (mL) of methylene chloride (methylene chloride) were placed in a round-bottom flask under nitrogen and cooled to-5 deg.C, and the intermediate 6-2 (2.8g, 7.6mmol) and NaOH (0.3g, 7.6mmol) dissolved in 5mL of a mixed solvent of methylene chloride/water (4 1v/v) was slowly added thereto while maintaining the temperature at low. After allowing the obtained mixture to react for 1 hour, the temperature was slowly increased, and the reaction was refluxed for one day. The reaction was cooled, the organic layer obtained therefrom was washed with water, and the solvent was removed therefrom to obtain intermediate 7 (1.37 g, yield 61% with respect to cyanuric chloride).
[ intermediate 7]
(3) Synthesis of Compound represented by the formula P-3
A compound represented by the formula P-3 was obtained in the same manner as the synthesis of the compound represented by the formula P-2 except that intermediate 7 (0.71g, 0.6 mmol) was used instead of intermediate 6-1 (1.2 g, yield 56% relative to intermediate 7).
[ chemical formula P-3]
1 H NMR (solvent): CDCl 3 )：7.52-7.33(m,30H),7.21-7.03(m,36H),6.46(m,12H),4.46-4.22(m,12H),4.06-3.99(m,6H),2.32(s,9H),1.96-0.89(m,60H)。
LC-Mass (liquid chromatography-Mass Spectrometry): 905m/z.
Comparative synthesis example 1: synthesis of Compound represented by the formula A-1
(1) A solution (100 ml (ml)) of 4,4'-dichlorobenzophenone (4, 4' -dichlorobenzophenone) [ manufactured by Tokyo Chemical Industry co., ltd. ] (10g, 90mmol) in N, N-dimethylformamide was cooled in an ice bath, sodium hydride (60%, 4.3g, 90mmol) was added thereto, the mixture was stirred, and N-ethylaniline (6.5g, 30mmol) was gradually added thereto. The mixture was stirred at room temperature for 5 hours, water was added thereto to perform dichloromethane extraction, and the extract obtained therefrom was purified by silica gel column chromatography to obtain a compound represented by the formula BP2 (3.1 g, yield 24%).
(2) The following reaction was performed under a nitrogen atmosphere. 32.2 parts by weight of potassium thiocyanate and 160.0 parts by weight of acetone were placed in a flask equipped with a cooling tube and a stirrer, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts by weight of 2-fluorobenzoic acid chloride (manufactured by tokyo chemical industries, ltd.) was added dropwise thereto over 10 minutes. When the addition was complete, the resulting mixture was stirred at room temperature for 2 hours. Subsequently, the reaction mixture was cooled, and 40.5 parts by weight of N-ethyl-o-toluidine (manufactured by tokyo chemical industries, ltd.) was added dropwise thereto. When the addition was complete, the resulting mixture was stirred at room temperature for 30 minutes. Subsequently, the reaction mixture was cooled, and 34.2 parts by weight of a 30% aqueous solution of sodium hydroxide was added dropwise thereto. When the addition was complete, the resulting mixture was stirred at room temperature for 30 minutes. Subsequently, 31.3 parts by weight of chloroacetic acid was added dropwise thereto at room temperature. When the addition was complete, the resulting mixture was stirred for 7 hours while heating and refluxing. Subsequently, the reaction mixture was cooled to room temperature, and then poured into 120.0 parts by weight of tap water, 200 parts by weight of toluene was added thereto, and the obtained mixture was stirred for 30 minutes. The stirring was stopped and the resultant was allowed to stand for 30 minutes to separate the organic layer from the aqueous layer. After separating and discarding the aqueous layer, the organic layer was washed with 200 parts by weight of hydrochloric acid, followed by 200 parts by weight of tap water and finally 200 parts by weight of saturated brine, and then filtered to obtain a dried organic layer. The obtained organic layer was treated using an evaporator (evaporator) to remove the solvent and obtain a lemon yellow liquid. The obtained lemon yellow liquid was purified by column chromatography. The purified lemon yellow liquid was dried at 60 ℃ under reduced pressure to obtain 49.9 parts by weight of the compound represented by chemical formula B-I-7 (yield 51%).
(3) The following reaction was performed under a nitrogen atmosphere. 7.6 parts by weight of the compound represented by the formula (B-I-7), 10.0 parts by weight of the compound represented by the formula BP2 and 20.0 parts by weight of toluene were put in a flask equipped with a cooling tube and a stirrer, 11.4 parts by weight of oxychloride was added thereto, and the mixture was stirred at 95 to 100 ℃ for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts by weight of isopropyl alcohol. Subsequently, the diluted reaction solution was poured into 300.0 parts by weight of a saturated salt solution, 100 parts by weight of toluene was added thereto, and the obtained mixture was stirred for 30 minutes. Subsequently, the stirring was stopped, and the resultant was allowed to stand for 30 minutes to separate an organic layer from an aqueous layer. After separating and discarding the aqueous layer, the organic layer was washed using 300 parts by weight of a saturated salt solution. To the organic layer was added an appropriate amount of sodium sulfate, and the obtained mixture was stirred for 30 minutes and then filtered to obtain a dried organic layer. The obtained organic layer was treated with an evaporator to distill and remove the solvent, thereby obtaining a bluish-violet solid. The bluish violet solid was purified by column chromatography. The purified bluish-violet solid was dried at 60 ℃ under reduced pressure to obtain 17.8 parts by weight of the compound represented by the formula A-II-16 (yield 100%).
LC-Mass (liquid chromatography-Mass Spectrometry): 715.3m/z.
(4) The following reaction was performed under a nitrogen atmosphere. 10.0 parts by weight of the compound represented by the formula (A-II-16), 5 parts by weight of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Industry Co., ltd.) and 30.0 parts by weight of N, N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirrer, and then stirred at 40 ℃ for 3 hours. Subsequently, the reaction mixture was cooled to room temperature and added dropwise to 500.0 parts by weight of tap water over 1 hour while stirring for 1 hour, to obtain a dark blue suspension. The obtained suspension was filtered to obtain a blue-green solid. The blue-green solid was further dried under reduced pressure at 60 ℃ to obtain 11.9 parts by weight of the compound represented by the formula A-1 (yield 90%) as a dye.
[ chemical formula A-1]
Comparative synthesis example 2: synthesis of Compound represented by the formula A-2
The compound represented by BP2 (1.03g, 2.45mmol) and intermediate 6 (0.9g, 2.45mmol) were placed in a round-bottomed flask under nitrogen, and 5.2g of toluene (tolumene) and POCl were added thereto 3 (1.50g, 9.8mmol), and the mixture was stirred for 5 hours while slowly heated to 110 ℃. When the reaction was completed, the temperature was lowered to room temperature, and an extract was obtained using Methyl Ethyl Ketone (MEK) and washed using 10% NaCl, water, and 10% HCl, respectively. After removing the organic layer, the residue was dried, lithium bis (trifluoromethyl) sulfonimide (1.2 g,4.2 mmol) was added thereto, 10g of dimethyl sulfoxide (DMSO) was added thereto, and the obtained mixture was stirred at room temperature for 30 minutes (anion exchange manufacturing). The reactant was dropped (dropping) into water to form a precipitate, and the precipitate was filtered and separated. The filtered solid compound was dissolved in 40g of acetonitrile (acetonitrile), 3g of activated carbon was added thereto, and the obtained mixture was stirred for 30 minutes. After removing the activated carbon through the filter, the filtrate obtained therefrom was removed by distillation and then dried to obtain the compound represented by chemical formula a-2 (2.01 g, yield 79%).
1 H NMR (solvent): CDCl 3 )：7.58-7.40(m,11H),7.22-7.03(m,11H),6.45(d,4H),4.53-4.44(m,1H),4.09(q,4H),2.31(s,3H),1.39(t,6H),1.18(d,12H)。
LC-Mass (liquid chromatography-Mass Spectrometry): 1049m/z.
[ chemical formula A-2]
Comparative synthesis example 3: synthesis of Compound represented by the formula A-3
(1) Synthesis of intermediate 8
KOH (10.4 g, 0.185mol), 170g of acetone (acetone) and 80g of water were placed in a round bottom flask and then stirred at room temperature, to which intermediate 5 (30g, 92.4 mmol) and iodoethane (iodoethane) (28.9g, 0.185mol) were added, respectively, and the mixture was stirred at 60 ℃ for 12 hours. When the reaction was completed, acetone (acetone) was removed by distillation, and an extract was obtained using dichloromethane (dichloromethane) and washed using 10% HCl and saturated sodium thiosulfate (sat. After removing the organic solvent, precipitation was performed using Ethyl acetate/Hexane (Ethyl acetate/Hexane) and intermediate 8 (26 g, 80% yield) was obtained.
[ intermediate 8]
1 H NMR (solvent): CDCl 3 )：7.45-7.26(m,8H),6.28(s,1H),3.94(q,2H),2.28(s,3H),1.34(t,3H)。
GC-MS：352m/z。
(2) Synthesis of Compound represented by the formula A-3
Intermediate 2 (1.29g, 2.45mmol) and intermediate 8 (0.86g, 2.45mmol) were placed in a round-bottomed flask under nitrogen, to which 6.5g of toluene (toluene) and POCl were added 3 (1.50g, 9.8mmol), and the mixture was slowly stirred for 5 hours while heating to 110 ℃. When the reaction was complete, the temperature was reduced to room temperature and methyl ethyl ketone (ME) was usedK) Extracts were obtained and washed with 10% NaCl, water and 10% HCl, respectively. After removing the organic layer, the residue was dried, lithium bis (trifluoromethyl) sulfonimide (1.2 g,4.2 mmol) was added thereto, 10g of dimethyl sulfoxide (DMSO) was added thereto, and the mixture was stirred at room temperature for 30 minutes (anion exchange manufacturing). The reactant was dropped (dropping) into water to form a precipitate, and the precipitate was separated by a filter. The filtered solid compound was dissolved in 4g of acetonitrile (acetonitrile), 3g of activated carbon was added thereto, and the obtained mixture was stirred for 30 minutes. The activated carbon was removed by a filter, and the filtrate obtained therefrom was removed by distillation, to obtain a compound represented by a-3 (2.41 g, yield 86%).
1 H NMR (solvent): CDCl 3 )：7.54-7.34(m,10H),7.23-7.18(m,4H),7.09-7.03(m,8H),6.43(d,4H),4.11(q,2H),4.00(t,4H),2.33(s,3H),1.96-1.80(m,8H),1.68-1.36(m,8H),1.20-1.08(m,7H)。
LC-Mass (liquid chromatography-Mass Spectrometry): 863m/z.
[ chemical formula A-3]
(examples)
Preparation of photosensitive resin composition
Each of the photosensitive resin compositions according to examples 1 to 3 and comparative examples 1 to 3 was prepared to have the composition shown in table 1. Specifically, a photopolymerization initiator was dissolved in a solvent, and the solution was stirred at room temperature for 2 hours. Then, a binder resin and a photopolymerizable monomer were added thereto, and the mixture was stirred at room temperature for 2 hours. Subsequently, a dye (pigment dispersion as the case may be) was added thereto, the mixture was stirred at room temperature for 1 hour, other additives were added thereto, and the obtained mixture was stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.
(Table 1)
(unit: wt%)
Adhesive resin
Acrylic binder resin (methacrylic acid/benzyl methacrylate =15/85 (w/w), weight average molecular weight =22,000g/mol, acid value =100 mgKOH/g).
Coloring agent
(dye P-1) Compound represented by the formula P-1
(dye P-2) Compound represented by the formula P-2
(dye P-3) Compound represented by the formula P-3
(dye A-1) Compound represented by the formula A-1
(dye A-2) Compound represented by the formula A-2
(dye A-3) Compound represented by the formula A-3
Photopolymerizable compounds
Dipentaerythritol hexaacrylate (DPHA)
Photopolymerization initiator
Oxe-01 is an oxime initiator (BASF Corp., ltd.)
Solvent(s)
Propylene Glycol Monomethyl Ether Acetate (PGMEA)
Other additives
Fluorine-based surfactant (Diegon Co., ltd., (Ltd.)), F-554 (10% diluted solution))
(evaluation)
Evaluation 1: evaluation of luminance and Heat resistance
By using a coater (Mikasa Co., ltd., (Ltd.)), photo coating (Opticoat) MS-A150) andthe photosensitive resin compositions according to examples 1 to 3 and comparative examples 1 to 3 were coated at a rotation speed (rpm) at which a predetermined thickness was obtained, respectively, on a hot-plate (hot-plate) at 90 ℃. Subsequently, the resultant was exposed to light at 50mJ/cm by using an exposure machine (Ushio Inc., youZhiwang Co., ltd.), HB-50110AA 2 The coated composition was exposed to light (millijoules per square centimeter) and baked in an oven at 230 ℃ for 30 minutes (after post-bake (PSB)) to complete the film sample. Color coordinates and brightness (Y) of the film samples were measured by using the MCPD 3000 apparatus before and after the oven baking, and the results are shown in table 2, and in addition, del (E)'s were calculated with reference to color coordinate changes before and after the post baking to evaluate heat resistance, and the results are shown in table 3.
Evaluation 2: evaluation of light resistance
The light fastness was evaluated by: the film sample in evaluation 1 was exposed to light at 60 ℃ for 2 hours using a xenon lamp (xenon lamp) (intensity of 0.68W (watt)), the color coordinates thereof were measured by using an MCPD 3000 (multi channel photo detector) colorimeter device, the color coordinates were converted into del (E) with reference to the change in color coordinates before and after post-baking (PSB), and the results are shown in table 2.
(Table 2)
(Table 3)
| Heat resistance | Light resistance | |
| Example 1 | 0.65 | 1.97 |
| Example 2 | 2.58 | 3.17 |
| Example 3 | 2.63 | 3.62 |
| Comparative example 1 | 8.84 | 6.59 |
| Comparative example 2 | 4.31 | 3.21 |
| Comparative example 3 | 1.69 | 3.98 |
Referring to tables 2 and 3, the photosensitive resin compositions according to examples 1 to 3 show excellent heat resistance and light resistance characteristics, compared to the photosensitive resin compositions according to comparative examples 1 to 3.
While the invention has been described in connection with what is presently considered to be practical exemplary 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.
Claims (22)
1. A compound comprising
A cation and an anion, and a salt thereof,
wherein the cation is represented by chemical formula 1:
[ chemical formula 1]
Wherein, in chemical formula 1,
R 1 to R 4 Independently a hydrogen atom, an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group or an unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 1 And R 2 One of which is necessarily unsubstituted C3 to C20 cycloalkyl, and R 3 And R 4 One of which is necessarily unsubstituted C3 to C20 cycloalkyl,
R 5 and R 6 Independently is a C3 to C20 alkyl group substituted with a C1 to C10 alkyl group, a C3 to C12 cycloalkyl group or a C6 to C12 aryl group substituted with a C1 to C20 alkyl group, with the proviso that R is 5 And R 6 One of which is necessarily a C3 to C20 alkyl group substituted with a C1 to C10 alkyl group, a C3 to C12 cycloalkyl group or a C6 to C12 aryl group,
R 7 is a C6 to C20 aryl group substituted with a halogen atom, an
X is O or S.
2. The compound of claim 1, wherein R 1 And R 2 And R 3 And R 4 One of them is necessarily an unsubstituted C5 to C20 cycloalkyl group.
3. The compound of claim 1, wherein the cation is represented by one of chemical formulas 1-1 through 1-3:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
Wherein, in chemical formulas 1-1 to 1-3,
R 1 and R 4 Independently an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, or an unsubstituted C2 to C20 heteroaryl group,
R 5 is a C6 to C20 aryl group substituted with a C1 to C20 alkyl group,
R 7 is a C6 to C20 aryl group substituted with a halogen atom,
R a 、R b 、R c and R d Independently is a hydrogen atom, and R 9 To R 11 Independently a hydrogen atom, an unsubstituted C1 to C10 alkyl group or an unsubstituted C6 to C12 aryl group, with the proviso that R 9 To R 11 Is an unsubstituted C1 to C10 alkyl group or an unsubstituted C6 to C12 aryl group,
x is O or S, and
a is adamantyl.
4. The compound of claim 1, wherein the cation is represented by one of chemical formula 1a to chemical formula 3 a:
[ chemical formula 1a ]
[ chemical formula 2a ]
[ chemical formula 3a ]
Wherein, in chemical formulas 1a to 3a,
R 1 and R 4 Independently an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, or an unsubstituted C2 to C20 heteroaryl group,
R a to R d Independently a hydrogen atom, and is a hydrogen atom,
R e and R f Independently a hydrogen atom or a halogen atom,
R g and R h Independently a hydrogen atom or an unsubstituted C1 to C20 alkyl group,
R e and R f At least one of which is a halogen atom,
R g and R h At least one of which is an unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom, an unsubstituted C1 to C10 alkyl group or an unsubstituted C6 to C12 aryl group,
R 9 to R 11 Is an unsubstituted C1 to C10 alkyl group,
x is O or S, and
a is adamantyl.
5. The compound of claim 4, wherein the cation is represented by one of chemical formulas 1-1a through 1-3 a:
[ chemical formula 1-1a ]
[ chemical formulas 1-2a ]
[ chemical formulas 1-3a ]
Wherein, in chemical formulas 1-1a to 1-3a,
R 1 and R 4 Independently an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, or an unsubstituted C2 to C20 heteroaryl group,
R a to R d Independently a hydrogen atom, and is a hydrogen atom,
R e and R f Independently a hydrogen atom or a halogen atom,
R e and R f At least one of which is a halogen atom,
R g is an unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom or an unsubstituted C1 to C10 alkyl group,
R 9 to R 11 Is an unsubstituted C1 to C10 alkyl group,
x is O or S, and
a is adamantyl.
6. The compound of claim 5, wherein the cation is represented by chemical formula 1-1 a-i to chemical formula 1-3 a-i:
[ chemical formula 1-1 a-I ]
[ chemical formula 1-2 a-I ]
[ chemical formulas 1-3 a-I ]
Wherein, in chemical formulas 1-1 a-I to 1-3 a-I,
R a to R d Independently a hydrogen atom, and is a hydrogen atom,
R e is a halogen atom, and is a halogen atom,
R g is an unsubstituted C1 to C20 alkyl group,
R 9 to R 11 Independently a hydrogen atom or an unsubstituted C1 to C10 alkyl group, R 9 To R 11 Is an unsubstituted C1 to C10 alkyl group,
x is O or S, and X is O or S,
R i to R l Independently is a hydrogen atom, an
A is adamantyl.
7. The compound of claim 6, wherein R e Is F or Cl.
8. The compound of claim 1, wherein the compound is represented by one of formulas 1-i through 1-v:
[ chemical formula 1-i ]
[ chemical formula 1-ii ]
[ chemical formulas 1-iii ]
[ chemical formulas 1-iv ]
[ chemical formula 1-v ]
Wherein, in chemical formulae 1-i to 1-v,
Y - is anionic, and
x is O or S.
9. The compound of claim 1, wherein the anion is represented by one selected from formula a to formula F:
[ chemical formula A ]
[ chemical formula B ]
[ chemical formula C ]
PW 12 O 40 3-
[ chemical formula D ]
SiW 12 O 40 4-
[ chemical formula E ]
CF 3 SO 3 -
[ chemical formula F ]
ClO 4 - 。
10. A compound represented by chemical formula 2:
[ chemical formula 2]
Wherein, in chemical formula 2,
R 21 to R 24 Independently a hydrogen atom, an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group or an unsubstituted C2 to C20 heteroaryl group, with the proviso that R is 21 And R 22 One of which is necessarily unsubstituted C3 to C20 cycloalkyl, and R 23 And R 24 One of which is necessarily unsubstituted C3 to C20 cycloalkyl,
R 25 is a C6 to C20 aryl group substituted with F or Cl,
R 26 is a C6 to C20 aryl group substituted with a C1 to C10 alkyl group,
L 1 is an unsubstituted C1 to C20 alkylene group,
x is O or S, and
Y - is an anion.
11. The compound of claim 10, wherein R 21 And R 22 One is an unsubstituted C3 to C20 cycloalkyl group and the other is an unsubstituted C6 to C20 aryl group, and
R 23 and R 24 One is an unsubstituted C3 to C20 cycloalkyl group and the other is an unsubstituted C6 to C20 aryl group.
12. The compound of claim 11, wherein the C3 to C20 cycloalkyl is cyclopentyl or cyclohexyl.
13. The compound of claim 10, wherein the compound represented by chemical formula 2 is represented by one of chemical formulae 2-i to 2-iv:
[ chemical formula 2-i ]
[ chemical formula 2-ii ]
[ chemical formula 2-iii ]
[ chemical formula 2-iv ]
Wherein, in chemical formulas 2-i to 2-iv,
x is O or S, and the compound is shown in the specification,
L 2 is unsubstituted C1 to C10 alkylene, and
Y - is an anion.
14. The compound of claim 10, wherein said Y - Represented by one selected from chemical formulas a to F:
[ chemical formula A ]
[ chemical formula B ]
[ chemical formula C ]
PW 12 O 40 3-
[ chemical formula D ]
SiW 12 O 40 4-
[ chemical formula E ]
CF 3 SO 3 -
[ chemical formula F ]
ClO 4 - 。
15. A compound represented by chemical formula 3:
[ chemical formula 3]
Wherein, in chemical formula 3,
R 31 to R 34 Independently a hydrogen atom, an unsubstituted C1 to C20 alkyl group, an unsubstituted C3 to C20 cycloalkyl group, an unsubstituted C6 to C20 aryl group, or an unsubstituted C2 to C20 heteroaryl group, with the proviso that R 31 And R 32 One of which is necessarily unsubstituted C3 to C20 cycloalkyl, and R 33 And R 34 One of which is necessarily unsubstituted C3 to C20 cycloalkyl,
R 35 is a C6 to C20 aryl group substituted with F or Cl,
R 36 is C1 to C20 alkyl substituted by C1 to C10 alkyl, and
L 3 is a trivalent linker group represented by the chemical formula L-3,
[ chemical formula L-3]
Wherein, in the chemical formula L-3,
L 4 is an unsubstituted C1 to C10 alkylene group,
x is O or S, and
Y - is an anion.
16. The compound of claim 15, wherein R 31 And R 32 One is unsubstituted C3 to C20 cycloalkyl and the other is unsubstituted C6 to C20 aryl, and
R 33 and R 34 One is an unsubstituted C3 to C20 cycloalkyl group and the other is an unsubstituted C6 to C20 aryl group.
17. The compound of claim 16, wherein the C3 to C20 cycloalkyl is cyclopentyl or cyclohexyl.
18. The compound of claim 15, wherein the compound represented by chemical formula 3 is represented by one of chemical formulae 3-iii to 3-v:
[ chemical formula 3-iii ]
[ chemical formula 3-iv ]
[ chemical formula 3-v ]
Wherein, in chemical formulas 3-iii to 3-v,
x is O or S, and
Y - is an anion.
19. The compound of claim 15, wherein said Y - Represented by one selected from chemical formulas A to F:
[ chemical formula A ]
[ chemical formula B ]
[ chemical formula C ]
PW 12 O 40 3-
[ chemical formula D ]
SiW 12 O 40 4-
[ chemical formula E ]
CF 3 SO 3 -
[ chemical formula F ]
ClO 4 - 。
20. A photosensitive resin composition comprising
The compound of any one of claims 1, 10 or 15,
a binder resin, and a binder resin,
a light-polymerizable compound which is a polymerizable compound,
a photopolymerization initiator, and
and (3) a solvent.
21. The photosensitive resin composition of claim 20, wherein the photosensitive resin composition further comprises a pigment.
22. A color filter produced using the photosensitive resin composition according to claim 20.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2016-0150593 | 2016-11-11 | ||
| KR20160150593 | 2016-11-11 | ||
| KR10-2017-0088432 | 2017-07-12 | ||
| KR1020170088432A KR102036682B1 (en) | 2016-11-11 | 2017-07-12 | Novel compound, photosensitive resin composition comprising the same and color filter |
| PCT/KR2017/007601 WO2018088670A1 (en) | 2016-11-11 | 2017-07-14 | Novel compound, photosensitive resin composition including same, and color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109803960A CN109803960A (en) | 2019-05-24 |
| CN109803960B true CN109803960B (en) | 2023-04-11 |
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| CN201780061147.3A Active CN109803960B (en) | 2016-11-11 | 2017-07-14 | Compound, photosensitive resin composition containing the same and color filter |
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| Country | Link |
|---|---|
| KR (1) | KR102036682B1 (en) |
| CN (1) | CN109803960B (en) |
| TW (1) | TWI644897B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08179465A (en) * | 1994-12-26 | 1996-07-12 | Konica Corp | Silver halide photographic sensitive material and development processing method |
| JP2011227408A (en) * | 2010-04-23 | 2011-11-10 | Toyo Ink Sc Holdings Co Ltd | Triallyl methane coloring agent and its usage |
| JP2012101048A (en) * | 2010-10-15 | 2012-05-31 | Sammy Corp | Slot machine |
| KR20140013967A (en) * | 2012-07-23 | 2014-02-05 | 동우 화인켐 주식회사 | Dyes for a color filter |
| CN105531327A (en) * | 2013-09-17 | 2016-04-27 | 富士胶片株式会社 | Curable coloring composition, cured film, color filter, method for manufacturing color filter, solid-state image pickup element, picture display device, and triarylmethane compound |
-
2017
- 2017-07-12 KR KR1020170088432A patent/KR102036682B1/en active IP Right Grant
- 2017-07-14 CN CN201780061147.3A patent/CN109803960B/en active Active
- 2017-10-16 TW TW106135224A patent/TWI644897B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08179465A (en) * | 1994-12-26 | 1996-07-12 | Konica Corp | Silver halide photographic sensitive material and development processing method |
| JP2011227408A (en) * | 2010-04-23 | 2011-11-10 | Toyo Ink Sc Holdings Co Ltd | Triallyl methane coloring agent and its usage |
| JP2012101048A (en) * | 2010-10-15 | 2012-05-31 | Sammy Corp | Slot machine |
| KR20140013967A (en) * | 2012-07-23 | 2014-02-05 | 동우 화인켐 주식회사 | Dyes for a color filter |
| CN105531327A (en) * | 2013-09-17 | 2016-04-27 | 富士胶片株式会社 | Curable coloring composition, cured film, color filter, method for manufacturing color filter, solid-state image pickup element, picture display device, and triarylmethane compound |
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| Publication number | Publication date |
|---|---|
| KR102036682B1 (en) | 2019-10-25 |
| TW201817715A (en) | 2018-05-16 |
| KR20180053218A (en) | 2018-05-21 |
| TWI644897B (en) | 2018-12-21 |
| CN109803960A (en) | 2019-05-24 |
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