CN112204466B - Photosensitive resin composition, photosensitive material, color filter and display device - Google Patents

Photosensitive resin composition, photosensitive material, color filter and display device Download PDF

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CN112204466B
CN112204466B CN201980035380.3A CN201980035380A CN112204466B CN 112204466 B CN112204466 B CN 112204466B CN 201980035380 A CN201980035380 A CN 201980035380A CN 112204466 B CN112204466 B CN 112204466B
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carbon atoms
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CN112204466A (en
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金惠陈
金汉修
李多美
梁承秦
李在容
崔相雅
金泳雄
白京林
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LG Chem Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Materials For Photolithography (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present specification provides photosensitive resin compositions, photosensitive materials, color filters, and display devices.

Description

Photosensitive resin composition, photosensitive material, color filter and display device
Technical Field
The present application claims priority from korean patent application No. 10-2018-0146367, filed to korean patent office on 11/23 in 2018, the entire contents of which are incorporated herein.
The present specification relates to a photosensitive resin composition, a photosensitive material, a color filter, and a display device.
Background
Currently, in order to realize a color filter, a pigment dispersion method using a pigment as a colorant is generally applied. However, in the pigment dispersion liquid, not only the pigment exists in a particle state to scatter light, but also the pigment surface area is drastically increased due to miniaturization of the pigment, and uneven pigment particles are generated due to deterioration of dispersion stability caused thereby. Therefore, in order to achieve high brightness, high contrast, and high resolution which have been demanded in recent years, a technique of using a dye instead of a pigment as a colorant has been studied in recent years.
In general, dyes have the advantage of high transmittance compared to pigments. However, there is a disadvantage that the heat resistance is insufficient compared with the pigment. Further, compared with the conventional pigment, the pigment has a disadvantage of insufficient chemical resistance because the solubility to an organic solvent is good.
Disclosure of Invention
Technical problem
The present specification provides photosensitive resin compositions, photosensitive materials, color filters, and display devices.
Solution to the problem
An embodiment of the present specification provides a photosensitive resin composition including a xanthene dye, a binder resin including one or more structures represented by chemical formulas 1 and/or 2 below, a polyfunctional monomer, a photoinitiator, and a solvent.
[ chemical formula 1]
[ chemical formula 2]
In the above-mentioned chemical formulas 1 and 2,
represents a moiety attached to other substituents or to a binding moiety,
x 'and X' are O or NH,
l1 to L4 and L3', equal to or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -C (=O) -, -L' -O (C=O) -, or-L '-O-L' -,
l ', L ' and L ' are the same or different from each other and are each independently a substituted or unsubstituted alkylene group, nx is hydrogen, a substituted or unsubstituted amine group, or a nitrile group,
t1 to T4 are identical to or different from each other and are each independently hydrogen, hydroxy, or substituted or unsubstituted alkyl,
t2 is an integer of 0 to 4, and when T2 is 2 or more, T2 is the same or different from each other,
t3 is an integer of 0 to 5, and when T3 is 2 or more, T3 is the same as or different from each other.
An embodiment of the present disclosure provides a photosensitive material manufactured using the photosensitive resin composition.
An embodiment of the present specification provides a color filter including the above photosensitive material.
An embodiment of the present specification provides a display device including the above color filter.
Effects of the invention
The photosensitive resin composition according to an embodiment of the present specification may be used as a colorant by comprising a binder resin containing one or more structures represented by chemical formulas 1 and/or 2, thereby being pad-dyedAnd excellent in the chemical resistance of elution.
Detailed Description
The present specification will be described in more detail below.
In this specification, when it is indicated that a certain member is located "on" another member, it includes not only the case where the certain member is in contact with the other member but also the case where another member exists between the two members.
In the present specification, when a certain component is referred to as "including" or "comprising" a certain component, unless otherwise specified, it means that other components may be further included, and not excluded.
In the present description of the invention,represents a site of binding to another substituent or binding moiety.
In the present specification, "derived unit" means a unit molecule or a repeating structure forming a polymer.
An embodiment of the present specification provides a photosensitive resin composition including a xanthene dye, a binder resin including one or more structures represented by chemical formulas 1 and/or 2 below, a polyfunctional monomer, a photoinitiator, and a solvent.
[ chemical formula 1]
[ chemical formula 2]
In the above-mentioned chemical formulas 1 and 2,
represents a moiety attached to other substituents or to a binding moiety,
x 'and X' are O or NH,
l1 to L4 and L3', equal to or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -C (=O) -, -L' -O (C=O) -, or-L '-O-L' -,
l ', L ' and L ' are identical to or different from each other and are each independently a substituted or unsubstituted alkylene group,
nx is hydrogen, a substituted or unsubstituted amino group, or a nitrile group,
t1 to T4 are identical to or different from each other and are each independently hydrogen, hydroxy, or substituted or unsubstituted alkyl,
t2 is an integer of 0 to 4, and when T2 is 2 or more, T2 is the same or different from each other,
t3 is an integer of 0 to 5, and when T3 is 2 or more, T3 is the same as or different from each other.
The photosensitive resin composition according to an embodiment of the present specification can improve the curing degree of a film by introducing the structure represented by the above chemical formula 1 into a binder resin and realizing self-crosslinking by exposure, and can improve the curing speed and efficiency by promoting the heat curing reaction between the cyclic ether structure and the carboxylic acid group contained in the binder resin by introducing the structure represented by the above chemical formula 2 into the binder resin, and can improve the curing degree of a film.
By including the structure represented by the above chemical formula 1 and the structure represented by the above chemical formula 2 in the above binder resin, since radicals according to the above chemical formula 1, radicals according to the above chemical formula 2, and the like are generated to generate sufficient radicals, photo-curing reactivity becomes high, and thus it is also possible to improve the curing degree of the film. That is, the photosensitive resin composition can improve the degree of crosslinking of the film and thus can improve the transfer by other solvents by including the binder resin having the structure represented by the above chemical formula 1 and the structure represented by the above chemical formula 2, as compared with the case where the binder resin having the structure represented by the above chemical formula 1 or 2 is included And dissolution, etc.
Specifically, the photosensitive resin composition including the binder resin including the structure represented by the above chemical formula 1 and the structure represented by the above chemical formula 2 is excellent in heat resistance and chemical resistance as compared with the photosensitive resin composition including the binder resin including the structure represented by the above chemical formula 2. This is because the structure represented by the above chemical formula 1 promotes the photocrosslinking reaction, and the structure represented by the above chemical formula 2 functions as a curing accelerator, so that the binder resin according to the present specification including the structure represented by the above chemical formula 1 and the structure represented by the above chemical formula 2 is excellent in heat resistance and chemical resistance when used in a photosensitive resin composition.
In the present specification, examples of substituents of the compound represented by the chemical formula are described below, but are not limited thereto.
In the present specification, the term "substituted or unsubstituted" means that it is selected from deuterium; a halogen group; a nitrile group; a nitro group; -OH; a carbonyl group; an ester group; -COOH; an imide group; an amide group; an alkoxy group; an alkyl group; cycloalkyl; alkenyl groups; a cycloalkenyl group; an arylalkyl group; a phosphine group; sulfonate; an amine group; an aryl group; heteroaryl; a silyl group; a boron base; an acryl group; an acrylate group; an ether group; a heterocyclic group containing 1 or more of N, O, S or P atoms and 1 or more of substituents in an anionic group, or not having any substituent.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine, and iodine.
In the present specification, the alkyl group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but the number of carbon atoms of the alkyl group may be 1 to 30. According to another embodiment, the above alkyl group has 1 to 20 carbon atoms. According to another embodiment, the above alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.
In the present specification, cycloalkyl is not particularly limited, but cycloalkyl having 3 to 30 carbon atoms is preferable, and in particular, cyclopentyl and cyclohexyl are preferable, but not limited thereto.
In the present specification, alkylene means a group having two binding sites on alkane (alkine). The alkylene group may be linear, branched or cyclic. The number of carbon atoms of the alkylene group is not particularly limited, and for example, the number of carbon atoms may be 1 to 30. Further, the number of carbon atoms may be 1 to 20, and the number of carbon atoms may be 1 to 10.
In the present specification, the cycloalkyl group is not particularly limited, but according to one embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like, but not limited thereto.
In the present specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as phenyl, biphenyl, and terphenyl, but is not limited thereto. The polycyclic aryl group may be naphthyl, anthracenyl, indenyl, phenanthryl, pyrenyl, perylenyl, triphenylenyl,A group, a fluorenyl group, etc., but is not limited thereto.
In the present specification, arylene means a group having two bonding positions on an aryl group, i.e., a 2-valent group. They are each a 2-valent group, and the above description of aryl groups can be applied.
In the present specification, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but the number of carbon atoms is 2 to 30, specifically, 2 to 20. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, and the like,Azolyl, (-) -and (II) radicals>Diazolyl, triazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, pyridazinyl, quinolinyl, isoquinolinyl, indolyl, carbazolyl, benzo- >Oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothiophenyl, benzofuranyl, dibenzofuranyl, and the like, but are not limited thereto.
In this specification, the heteroaryl group is aromatic, and the above description of the heterocyclic group can be applied thereto.
In the present specification, the above-mentioned alkoxy group may be a straight chain or branched chain, and the number of carbon atoms is not particularly limited, but may be 1 to 30, specifically 1 to 20, more specifically 1 to 10.
In the present specification, the amine group may be selected from the group consisting of-NH 2 The alkyl amine group, the N-alkylaryl amine group, the aryl amine group, the N-arylheteroaryl amine group, the N-alkylheteroaryl amine group and the heteroaryl amine group are not particularly limited, but are preferably 1 to 30 in carbon number. Specific examples of the amine group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamine group, a naphthylamino group, a biphenylamino group, an anthracenylamino group, a 9-methyl-anthracenylamino group, a diphenylamino group, an N-phenylnaphthylamino group, a xylylamino group, an N-phenyltolylamino group, a triphenylamino group, an N-phenylbiphenylamino group, an N-phenylnaphthylamino group, an N-biphenylnaphthylamino group, an N-naphthylfluorenylamino group, an N-phenylphenanthrylamino group, an N-biphenylphenanthrenylamino group, an N-phenylfluorenylamino group, an N-biphenylfluorenylamino group, and the like, but are not limited thereto.
In the present specification, the anionic group has a chemical bond with the structure of chemical formula 1, and the above chemical bond may be referred to as an ionic bond. The anionic group is not particularly limited, and for example, anions described in U.S. Pat. No. 7,939,644, japanese patent application laid-open No. 2006-003080, japanese patent application laid-open No. 2006-001917, japanese patent application laid-open No. 2005-159926, japanese patent application laid-open No. 2007-7028897, japanese patent application laid-open No. 2005-071680, korean application laid-open No. 2007-7000693, japanese patent application laid-open No. 2005-111696, japanese patent application laid-open No. 2008-249663, and Japanese patent application laid-open No. 2014-199436 can be used.
Specific examples of the anionic group include trifluoromethanesulfonate anions; bis (trifluoromethylsulfonyl) amide anion; bis-trifluoromethanesulfonyl imide anions; biperfluoroethylsulfonimide anions; tetraphenylborate anions; tetrakis (4-fluorophenyl) borate; tetrakis (pentafluorophenyl) borate; tris (trifluoromethanesulfonyl) methide; SO (SO) 3 - ；CO 2 - ；SO 2 N - SO 2 CF 3 ；SO 2 N - SO 2 CF 2 CF 3 The method comprises the steps of carrying out a first treatment on the surface of the Halogen groups such as fluorine groups, iodine groups, chlorine groups, and the like, but are not limited thereto.
In the present specification, the anionic group may itself have an anion, or may exist in the form of a complex together with other cations. Thus, the sum of the overall charges of the molecules of the compounds of the present invention may vary depending on the number of substituted anionic groups. Since the compound of the present invention has a cation in one amine group, the sum of the overall charges of the molecules may have a value of an anion to 0, which is a value obtained by subtracting 1 from the number of substituted anionic groups.
In the present specification, "(meth) acrylic acid [ (" acrylic acid ")(meth) acrylic acid) means at least one selected from acrylic acid and methacrylic acid. "(meth) acrylic acid (> The expression "meth) acrylic acid" also has the same meaning.
In one embodiment of the present specification, the binder resin containing one or more structures represented by the above chemical formulas 1 and/or 2 further contains a unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.
The unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms may have any of the following structures, but is not limited thereto.
In the above structure, R is hydrogen, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms,
x3 and X4 are the same or different and each is a direct bond, -Rz-O-, -Rz-S-, or-Rz-NH-, wherein Rz is a substituted or unsubstituted alkanediyl group having 1 to 6 carbon atoms.
In one embodiment of the present specification, R may be an alkyl group substituted with —oh having 1 to 4 carbon atoms.
In the present specification, the above photosensitive resin composition further comprises a binder resin containing a unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.
The above-mentioned unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms can be applied to the above description.
The binder resin containing a unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms may be an epoxy-based binder resin.
In one embodiment of the present specification, the xanthene dye is represented by the following chemical formula 3.
[ chemical formula 3]
In the above-mentioned chemical formula 3, a compound represented by formula 1,
r1 to R6 are the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, nitro, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,
r7 to R11 are the same or different from each other and are each independently selected from hydrogen, deuterium, -OH, -SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COOH、-COO - Z + 、-COORa、-SO 3 Rb、-SO 2 NRcRd, -CONRe, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,
Z + represents [ N (Rf) 4 ] + 、Na + Or K + ，
Ra and Rb are the same or different from each other and are each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group,
rc to Re are the same or different from each other and are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,
Rc and Rd optionally combine with each other to form a heterocyclic ring containing a nitrogen atom,
the Rf may be the same or different,
at least one of the above R7 to R11 is-SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COO - Z + 、-COORa、-SO 3 Rb, or-SO 2 NRcRd，
R12 to R15 are the same or different from each other and are each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl,
q1 and Q2 are the same or different from each other and are each independently a direct bond, or a substituted or unsubstituted alkylene group,
rx is an anionic group or an ammonium structure,
a is 0 or 1.
In one embodiment of the present specification, R1 to R6 are the same or different from each other and are each independently selected from hydrogen, deuterium, a halogen group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R1 to R6 are the same or different from each other and are each independently selected from hydrogen, deuterium, a halogen group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
In one embodiment of the present specification, R1 to R6 are the same or different from each other and are each independently selected from hydrogen, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
In one embodiment of the present description, R1 to R6 are hydrogen, or substituted or unsubstituted methyl.
In one embodiment of the present description, R1 to R6 are hydrogen, or methyl.
In one embodiment of the present specification, R7 to R11 are the same or different from each other and are each independently selected from hydrogen, deuterium, -OH, -SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COOH、-COO - Z + 、-COORa、-SO 3 Rb、-SO 2 NRcRd, -CONRe, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R7 to R11 are the same or different from each other and are each independently selected from hydrogen, deuterium, -OH, -SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COOH、-COO - Z + 、-COORa、-SO 3 Rb、-SO 2 NRcRd, -CONRe, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkyl having 6 to 20 carbon atomsOr unsubstituted aryl, and substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms.
In one embodiment of the present specification, R7 to R11 are the same or different from each other and are each independently selected from hydrogen, -SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COO - Z + 、-COORa、-SO 3 Rb, and-SO 2 NRcRd。
In one embodiment of the present specification, R7 to R11 are the same or different from each other and are each independently selected from hydrogen, -SO 3 - 、-SO 3 H、-COO - 、-COO - Z + and-COORa.
In one embodiment of the present specification, Z + Is [ N (Rf) 4 ] + 、Na + Or K + 。
In one embodiment of the present specification, Z + Is Na (Na) + 。
In an embodiment of the present specification, ra to Re are the same or different from each other, each is independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, rc and Rd may be combined with each other to form a heterocyclic ring containing a nitrogen atom, and Rf may be the same or different.
In an embodiment of the present specification, ra to Re are the same or different from each other, each is independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, rc and Rd may be combined with each other to form a heterocyclic ring containing a nitrogen atom, and Rf may be the same or different.
In an embodiment of the present specification, ra to Re are the same or different from each other, each independently is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, rc and Rd may be combined with each other to form a heterocyclic ring containing a nitrogen atom, and Rf may be the same or different.
In one embodiment of the present specification, ra is substituted or unsubstituted methyl.
In one embodiment of the present specification, ra is methyl.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen or a straight or branched alkyl group having 3 to 20 carbon atoms.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen or branched alkyl of 3 to 20 carbon atoms.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
In one embodiment of the present specification, rc and Rd are the same or different from each other and are each independently hydrogen or a straight or branched alkyl group having 1 to 10 carbon atoms.
In one embodiment of the present specification, rc and Rd are the same or different from each other and are each independently hydrogen or branched alkyl having 1 to 10 carbon atoms.
In one embodiment of the present specification, rc and Rd are the same or different from each other and are each independently hydrogen, or substituted or unsubstituted 2-ethylhexyl.
In one embodiment of the present description, rc and Rd are the same or different from each other and are each independently hydrogen, or 2-ethylhexyl.
In one embodiment of the present description, -SO 2 NRcRd may be composed of-SO 2 NHY represents that the definition of Rc and Rd can be applied to Y.
In one embodiment of the present specification, R12 to R15 are the same or different from each other and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
In one embodiment of the present specification, R12 to R15 are the same or different from each other and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.
In one embodiment of the present specification, R12 to R15 are the same or different from each other and are each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.
In one embodiment of the present specification, R12 and R14 are the same or different from each other, and are each independently hydrogen, substituted or unsubstituted ethyl, or substituted or unsubstituted propyl.
In one embodiment of the present specification, R12 and R14 are the same or different from each other, each independently hydrogen, ethyl, n-propyl or isopropyl.
In one embodiment of the present specification, R13 and R15 are the same or different from each other, and are each independently a substituted or unsubstituted ethyl group, or a substituted or unsubstituted phenyl group.
In one embodiment of the present specification, R13 and R15 are the same or different from each other, each independently is ethyl; or is selected from methyl, -SO 2 NHY、-SO 3 - and-SO 3 H is one or more substituted phenyl groups, and Y is the same as described above.
In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.
In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.
In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
In one embodiment of the present specification, Q1 and Q2 are the same or different from each other, and are each independently a direct bond, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group.
In one embodiment of the present description, Q1 and Q2 are the same or different from each other and are each independently a direct bond, methylene, ethylene, or propylene.
In one embodiment of the present specification, rx is an anionic group or an ammonium structure.
In one embodiment of the present disclosure, rx is an anionic group, which is a chloride group (Cl) - )。
In one embodiment of the present specification, rx is an ammonium structure, which may be represented by the following chemical formula a.
[ chemical formula A ]
In the above-mentioned chemical formula a,
a1 to A4 are the same or different from each other and are each independently hydrogen, or a substituted or unsubstituted alkyl group.
In one embodiment of the present specification, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In one embodiment of the present specification, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
In one embodiment of the present specification, A1 to A4 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.
In one embodiment of the present description, a is 0 or 1.
In one embodiment of the present description, a is 0.
In one embodiment of the present description, a is 1.
In one embodiment of the present specification, the chemical formula 3 may have any one of the following structures.
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In the above structure, Y is a branched alkyl group having 3 to 20 carbon atoms. Specifically, Y is 2-ethylhexyl.
In the above structure, byThe meaning of the indicated structure is in +.>Any of the carbon atoms of the phenyl group containing a moiety other than that substituted with a methyl group may be substituted with-SO 2 NHY。
In the above structure, byThe meaning of the indicated structure is in +.>Any of the carbon atoms of the phenyl group containing a moiety other than that substituted with a methyl group may be substituted with-SO 3 - 。
In one embodiment of the present description, X 'and X' are the same or different from each other and are O or NH.
In one embodiment of the present disclosure, X' is O.
In one embodiment of the present description, X "is O.
In one embodiment of the present disclosure, X' is NH.
In one embodiment of the present description, X "is NH.
In an embodiment of the present specification, L1 to L4 and L3', equal to or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, -C (=o) -, -L ' -O (c=o) -, or-L "-O-L '" -.
In an embodiment of the present specification, L1 to L4 and L3', which are the same or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group of 1 to 30 carbon atoms, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms, -C (=o) -, -L ' -O (c=o) -, or-L "-O-L '" -.
In an embodiment of the present specification, L1 to L4 and L3', which are the same or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms, a substituted or unsubstituted arylene group of 6 to 20 carbon atoms, -C (=o) -, -L ' -O (c=o) -, or-L "-O-L '" -.
In an embodiment of the present specification, L1 to L4 and L3', which are the same or different from each other, are each independently a direct bond, a substituted or unsubstituted alkylene group of 1 to 10 carbon atoms, a substituted or unsubstituted arylene group of 6 to 12 carbon atoms, -C (=o) -, -L ' -O (c=o) -, or-L "-O-L '" -.
In one embodiment of the present description, L1 is a direct bond, a substituted or unsubstituted alkylene, or-C (=o) -.
In one embodiment of the present description, L1 is a direct bond, a substituted or unsubstituted alkylene group of 1 to 30 carbon atoms, or-C (=o) -.
In one embodiment of the present description, L1 is a direct bond, a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms, or-C (=o) -.
In one embodiment of the present description, L1 is a direct bond, a substituted or unsubstituted alkylene group of 1 to 10 carbon atoms, or-C (=o) -.
In one embodiment of the present disclosure, L1 is a direct bond.
In one embodiment of the present specification, L1 is a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, or a substituted or unsubstituted propylene group.
In one embodiment of the present specification, L1 is methylene, ethylene, or propylene.
In one embodiment of the present description, L1 is-C (=o) -.
In one embodiment of the present description, L2 is a direct bond, -C (=o) -, or-L' -O (c=o) -.
In one embodiment of the present disclosure, L2 is a direct bond.
In one embodiment of the present description, L2 is-C (=o) -.
In one embodiment of the present specification, L2 is-L' -O (c=o) -.
In one embodiment of the present description, L ', L ", and L'" are the same or different from each other and are each independently a substituted or unsubstituted alkylene.
In one embodiment of the present specification, L' is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.
In one embodiment of the present specification, L' is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.
In one embodiment of the present specification, L' is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
In one embodiment of the present description, L' is a substituted or unsubstituted methylene.
In one embodiment of the present description, L' is methylene.
In one embodiment of the present description, L3 'and L4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or-L "-O-L'" -.
In one embodiment of the present description, L3' and L4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or-L ' -O-L ' -.
In one embodiment of the present description, L3' and L4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or-L ' -O-L ' -.
In one embodiment of the present description, L3' and L4 are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, or-L ' -O-L ' -.
In one embodiment of the present description, L3 is a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, or-L "-O-L'" -.
In one embodiment of the present specification, L3 is ethylene, propylene, butylene, or-L '-O-L' -.
In one embodiment of the present description, L "and L'" are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.
In one embodiment of the present specification, L "and L'" are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.
In one embodiment of the present description, L "and L'" are the same or different from each other and are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
In one embodiment of the present description, L "and L'" are the same or different from each other and are each independently a substituted or unsubstituted methylene group or a substituted or unsubstituted ethylene group.
In one embodiment of the present description, L "and L'" are the same or different from each other and are each independently methylene or ethylene.
In one embodiment of the present disclosure, nx is hydrogen, a substituted or unsubstituted amine group, or a nitrile group.
In one embodiment of the present disclosure, nx is hydrogen.
In one embodiment of the present disclosure, nx is a nitrile group.
In one embodiment of the present disclosure, nx is-NH 2 Or a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms.
In one embodiment of the present disclosure, nx is-NH 2 Or a substituted or unsubstituted alkylamino group having 1 to 20 carbon atoms.
In one embodiment of the present disclosure, nx is-NH 2 Or a substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms.
In one embodiment of the present disclosure, nx is-NH 2 A substituted or unsubstituted dimethylamino group, or a substituted or unsubstituted diethylamino group.
In one embodiment of the present disclosure, nx is-NH 2 A dimethylamino group, or a diethylamino group.
In one embodiment of the present specification, T1 to T4 are the same or different from each other, and are each independently hydrogen, hydroxyl, or substituted or unsubstituted alkyl of 1 to 30 carbon atoms.
In one embodiment of the present specification, T1 to T4 are the same or different from each other, and are each independently hydrogen, hydroxyl, or substituted or unsubstituted alkyl of 1 to 20 carbon atoms.
In one embodiment of the present specification, T1 to T4 are the same or different from each other, and are each independently hydrogen, hydroxyl, or substituted or unsubstituted alkyl of 1 to 10 carbon atoms.
In one embodiment of the present specification, T1 to T4 are the same or different from each other, and are each independently hydrogen, hydroxy, substituted or unsubstituted methyl.
In one embodiment of the present description, T1 is hydrogen, or methyl.
In one embodiment of the present description, T2 is hydrogen.
In one embodiment of the present description, T3 is hydrogen, hydroxy, or methyl substituted with amino.
In one embodiment of the present description, T4 is hydrogen, or methyl.
According to an embodiment of the present specification, the above chemical formula 1 may be represented by the following chemical formula 1-1.
[ chemical formula 1-1]
In the above-mentioned chemical formula 1-1,
represents a moiety attached to other substituents or to a binding moiety,
X', L1, L2, T1 to T3, T2 and T3 are as defined in chemical formula 1 above.
In one embodiment of the present specification, the chemical formula 1 may be represented by any one of the following structures, but is not limited thereto. Chemical formula 1 above forms a moiety polymerized from any of the following structures.
In one embodiment of the present specification, the above chemical formula 2 may be represented by the following chemical formula 2-1.
[ chemical formula 2-1]
In the above chemical formula 2-1, X ", L3, L4 and T4 are as defined in the above chemical formula 2,
t5 and T6 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group.
In one embodiment of the present specification, T5 and T6 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In one embodiment of the present specification, T5 and T6 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
In one embodiment of the present specification, T5 and T6 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
In one embodiment of the present specification, T5 and T6 are the same or different from each other, each independently hydrogen, substituted or unsubstituted methyl, or substituted or unsubstituted ethyl.
In one embodiment of the present description, T5 and T6 are the same or different from each other, each independently hydrogen, methyl, or ethyl.
In one embodiment of the present specification, the chemical formula 2 may be represented by the following structure, but is not limited thereto. Chemical formula 2 above forms a moiety polymerized from any of the following structures.
In one embodiment of the present specification, the binder resin may further contain one or more structures represented by any one of the following chemical formulas 4 to 6.
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
In the above-mentioned chemical formulas 4 to 6,
represents a moiety attached to other substituents or to a binding moiety,
l41, L41', L51, L52 and L61 are identical to or different from each other and are each independently a direct bond or a substituted or unsubstituted alkylene group,
x1, X2, Y1, Y2 and Z1 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group,
x2 is an integer of 0 to 11, and when X2 is 2 or more, X2 are the same or different from each other,
y2 is an integer of 0 to 5, and Y2 is the same as or different from each other when Y2 is 2 or more.
In one embodiment of the present specification, L41', L51, L52 and L61 are the same or different from each other, and each is independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.
In one embodiment of the present specification, L41', L51, L52 and L61 are the same or different from each other, and each is independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.
In one embodiment of the present specification, L41', L51, L52 and L61 are the same or different from each other, and each is independently a direct bond, or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
In one embodiment of the present description, L41', L51, L52 and L61 are the same or different from each other, each independently being a direct bond, a substituted or unsubstituted methylene group.
In one embodiment of the present description, L41', L51, L52 and L61 are the same or different from each other, each independently being a direct bond, methylene.
In one embodiment of the present specification, X1, X2, Y1, Y2 and Z1 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In one embodiment of the present specification, X1, X2, Y1, Y2 and Z1 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
In one embodiment of the present specification, X1, X2, Y1, Y2 and Z1 are the same or different from each other, and are each independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
In one embodiment of the present description, X1, X2, Y1, Y2 and Z1 are the same or different from each other, each independently is hydrogen, or a substituted or unsubstituted methyl group.
In one embodiment of the present description, X1, X2, Y1, Y2 and Z1 are the same or different from each other and are each independently hydrogen or methyl.
In one embodiment of the present specification, the chemical formula 4 may be represented by the following structure, but is not limited thereto.
In one embodiment of the present specification, the chemical formula 5 may be represented by the following structure, but is not limited thereto.
In one embodiment of the present specification, the chemical formula 6 may be represented by the following structure, but is not limited thereto.
An embodiment of the present disclosure provides a photosensitive resin composition, including, based on the total weight of the photosensitive resin composition: 0.1 to 30% by weight of the above xanthene dye; 1 to 40% by weight of a binder resin containing one or more structures represented by the above chemical formulas 1 and/or 2; 1 to 40 weight percent of a polyfunctional monomer; 0.1 to 10 wt% of a photoinitiator; and the balance of solvent.
In one embodiment of the present specification, the remaining amount of the solvent may be 60 to 90 wt% based on the total weight of the photosensitive resin composition.
By satisfying the above ranges for the respective constituent elements of the photosensitive resin composition, a color composition for color filters excellent in heat resistance and chemical resistance can be obtained.
In one embodiment of the present specification, the weight average molecular weight of the binder resin is 5000 to 30000g/mol. Preferably, it may be 5000 to 20000g/mol.
The binder resin satisfies the weight average molecular weight range, whereby a color filter film excellent in heat resistance and chemical resistance can be obtained.
The weight average molecular weight is one of average molecular weights used based on the molecular weight of a certain polymer substance, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution in weight fractions.
The weight average molecular weight may be determined by Gel Permeation Chromatography (GPC) analysis.
In one embodiment of the present specification, the photosensitive resin composition may further include one selected from pigments and dyes.
That is, the photosensitive resin composition may contain at least 1 of a dye and a pigment in addition to the xanthene dye. For example, the photosensitive resin composition may contain only the xanthene dye, but may contain the xanthene dye and 1 or more dyes; or may contain the above xanthene dye and 1 or more pigments; or may contain the above xanthene dye, 1 or more dyes, and 1 or more pigments.
In one embodiment of the present specification, the Pigment and dye may be a phthalocyanine-based, anthraquinone-based, azaporphyrin-based, azo-based, triarylmethane-based, dipyrrolopyrrole-based, blue Pigment, or violet Pigment (Pigment violet) 23, but is not limited thereto.
According to one embodiment of the present disclosure, the pigment may be c.i. pigment blue 15:6.
Specifically, the pigment further contained in the photosensitive resin composition may be 1 to 10% by weight based on the total weight of the photosensitive resin composition.
The dye and pigment may be selected from metal-complex compounds, azo (azo) compounds, metal azo (metal azo) compounds, quinophthalone (quinophthalone) compounds, isoindoline (isoindoline) compounds, methine (metafine) compounds, phthalocyanine (phthalocyanine) compounds, metal phthalocyanine (metal phthalocyanine) compounds, porphyrin (porphyrin) compounds, metalloporphyrin (metal porphyrin) compounds, tetraazaporphyrin (tetra aza porphyrin) compounds, metal tetraazaporphyrin (metal tetra aza porphyrin) compounds, cyanine (Cyanine) compounds, xanthene (Xanthene) compounds, borodipyrromethane (boron dipyrromethane) compounds, dipyrromethane (metal dipyrromethane) compounds, anthraquinone (anthraquinone) compounds, pyrrolopyrrole (pyrrolopyrrole) compounds, perylene (perylene) compounds, and perylene (trisene) compounds.
The binder resin may be a copolymer resin of a polyfunctional monomer imparting mechanical strength and an alkali-soluble monomer, and may further contain a binder commonly used in the art.
The polyfunctional monomer imparting mechanical strength to the film may be any one or more of unsaturated carboxylic acid esters, aromatic vinyl groups, unsaturated ethers, unsaturated imides, and acid anhydrides.
Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy (meth) acrylate, P-nonylphenoxy polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1, 3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl alpha-hydroxy methacrylate, ethyl alpha-hydroxy methacrylate, propyl alpha-hydroxy methacrylate, and butyl alpha-hydroxy methacrylate, but are not limited thereto.
Specific examples of the aromatic vinyl monomers include, but are not limited to, styrene, α -methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, and (o, m, p) -chlorostyrene.
Specific examples of the unsaturated ethers include, but are not limited to, vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether.
Specific examples of the unsaturated imides may be selected from N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide, but are not limited thereto.
Examples of the acid anhydride include maleic anhydride, methyl maleic anhydride, tetrahydrophthalic anhydride, and the like, but are not limited thereto.
The alkali-solubility-imparting monomer is not particularly limited as long as it contains an acid group, and for example, one or more selected from (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono-2- ((meth) acryloyloxy) ethyl phthalate, mono-2- ((meth) acryloyloxy) ethyl succinate, and ω -carboxyl polycaprolactone mono (meth) acrylate is preferably used, but not limited thereto.
According to an embodiment of the present specification, the acid value of the binder resin may be 50 to 150mgKOH/g.
The acid value of the binder resin may be measured by titration with a 0.1N potassium hydroxide (KOH) methanol solution.
The photoinitiator is not particularly limited as long as it is an initiator that triggers crosslinking by generating free radicals by light, and may be, for example, 1 or more selected from acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and oxime-based compounds.
Examples of the acetophenone-based compound include, but are not limited to, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromo-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one.
Examples of the bisimidazole compound include 2, 2-bis (2-chlorophenyl) -4,4', 5' -tetraphenylbisimidazole and 2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetrakis (3, 4, 5-trimethoxyphenyl) -1,2' -biimidazole, 2 '-bis (2, 3-dichlorophenyl) -4,4',5 '-tetraphenyl biimidazole, 2' -bis (o-chlorophenyl) -4, 5 '-tetraphenyl-1, 2' -biimidazole, and the like, but are not limited thereto.
The triazine compound may be 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 1, 3-hexafluoroisopropyl-3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid ester, ethyl 2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetic acid ester, 2-epoxyethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetic acid ester, cyclohexyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetic acid ester benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetic acid ester, 3- { chloro-4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanamide, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1, 3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, etc., but is not limited thereto.
Examples of the oxime-based compound include, but are not limited to, 1- (4-phenylthio) phenyl-1, 2-octanedione-2- (O-benzoyl oxime) (CIBA-GEIGY corporation, CGI 124), 1- (9-ethyl) -6- (2-methylbenzoyl-3-yl) -ethanone-1- (O-acetyl oxime) (CGI 242), and N-1919 (ADECA corporation).
The solvent is selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, and 1, 4-diAlkane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1, 2-dichloroethane, 1-trichloroethane, 1, 2-trichloroethylene, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, tert-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycolEther acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.
In one embodiment of the present specification, the solvent may be propylene glycol monomethyl ether acetate and/or 3-methoxybutyl acetate.
In one embodiment of the present invention, the content of the xanthene dye is 0.1 to 30 wt%, the content of the binder resin is 1 to 40 wt%, and the content of the photoinitiator is 0.1 to 10 wt%, based on the total weight of solid components in the photosensitive resin composition.
When each component contained in the photosensitive resin composition satisfies the above range, the photosensitive resin composition has an effect of excellent heat resistance and chemical resistance, based on the total weight of solid components in the photosensitive resin composition.
The total weight of the solid components is the sum of the total weights of the components other than the solvent in the photosensitive resin composition. The basis of the solid content and the weight% of the solid content of each component can be measured by a conventional analytical means used in the art such as liquid chromatography or gas chromatography.
According to an embodiment of the present disclosure, the photosensitive resin composition further includes 1 or 2 or more additives selected from the group consisting of antioxidants, adhesion promoters, polythiol agents, photocrosslinking sensitizers, curing accelerators, adhesion promoters, surfactants, thermal polymerization inhibitors, ultraviolet absorbers, dispersants, and leveling agents.
In the present specification, the photosensitive resin composition may further contain an antioxidant, a surfactant, a polythiol agent, and an adhesion promoter.
According to an embodiment of the present disclosure, the additive is contained in an amount of 0.1 to 10 wt% based on the total weight of the photosensitive resin composition.
According to an embodiment of the present disclosure, the additive is contained in an amount of 0.1 to 10% by weight based on the total weight of solid components in the photosensitive resin composition. The photocrosslinking sensitizer may be a benzophenone compound selected from the group consisting of benzophenone, 4-bis (dimethylamino) benzophenone, 4-bis (diethylamino) benzophenone, 2,4, 6-trimethylaminobenzophenone, methyl o-benzoylbenzoate, 3-dimethyl-4-methoxybenzophenone, and 3, 4-tetra (t-butylperoxycarbonyl) benzophenone; fluorenone compounds such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone; thioxanthone compounds such as thioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, and diisopropylthioxanthone; xanthone compounds such as xanthone and 2-methylxanthone; anthraquinone compounds such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, t-butylanthraquinone, and 2, 6-dichloro-9, 10-anthraquinone; acridine compounds such as 9-phenylacridine, 1, 7-bis (9-acridinyl) heptane, 1, 5-bis (9-acridinyl pentane), and 1, 3-bis (9-acridinyl) propane; dicarbonyl compounds such as benzil, 1, 7-trimethyl-bicyclo [2, 1] heptane-2, 3-dione, and 9, 10-phenanthrenequinone; phosphine oxide compounds such as 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide; benzoate compounds such as methyl 4- (dimethylamino) benzoate, ethyl 4- (dimethylamino) benzoate, and 2-n-butoxyethyl 4- (dimethylamino) benzoate; amino synergists such as 2, 5-bis (4-diethylaminobenzylidene) cyclopentanone, 2, 6-bis (4-diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4-diethylaminobenzylidene) -4-methyl-cyclopentanone, and the like; coumarin compounds such as 3, 3-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, and 10, 10-carbonylbis [1, 7-tetramethyl-2, 3,6, 7-tetrahydro-1 h,5h,11h-C1] -benzopyrano [6,7,8-ij ] -quinolizin-11-one; chalcone compounds such as 4-diethylaminochalcone and 4-azidobenzoyl acetophenone; 2-benzoylmethylene; more than 1 of 3-methyl-b-naphthothiazoline.
The above curing accelerator is used for curing and improving mechanical strengthSpecifically, a compound selected from the group consisting of 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzo can be usedMore than 1 of oxazole, 2, 5-dimercapto-1, 3, 4-thiadiazole, 2-mercapto-4, 6-dimethylaminopyridine, pentaerythritol-tetrakis (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercaptoacetate), pentaerythritol-tris (2-mercaptoacetate), trimethylolpropane-tris (2-mercaptoacetate), and trimethylolpropane-tris (3-mercaptopropionate).
As the adhesion promoter used in the present specification, 1 or more kinds of methacryloyl silane coupling agents selected from methacryloxypropyl trimethoxy silane, methacryloxypropyl triethoxy silane, methacryloxypropyl dimethoxy silane and the like can be used, and as the alkyl trimethoxy silane, 1 or more kinds selected from octyl trimethoxy silane, dodecyl trimethoxy silane, octadecyl trimethoxy silane and the like can be used.
The bonding aid may be a bonding aid commonly used in the art, and in one embodiment, the bonding aid may be KBM-503.
The above-mentioned surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, a silicone-based surfactant may be used, for example, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc., as a fluorine-based surfactant, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. of DIC (DaiNippon Ink & Chemicals) may be used, but are not limited thereto.
In one embodiment of the present specification, the surfactant may be a fluorine-based surfactant, specifically, F-554 of DIC company.
The antioxidant may be 1 or more selected from Hindered phenol (Hindered phenol) antioxidants, amine antioxidants, sulfur antioxidants and phosphine antioxidants, but is not limited thereto.
Specific examples of the antioxidant include phosphoric acid-based heat stabilizers such as phosphoric acid, trimethyl phosphate, and triethyl phosphate; hindered antioxidants such as 2, 6-di-tert-butyl-p-cresol, octadecyl-3- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, diethyl 3, 5-di-tert-butyl-4-hydroxybenzyl phosphite, 2-thiobis (4-methyl-6-tert-butylphenol), 2,6-g, t-butylphenol, 4 '-butylidenebis (3-methyl-6-tert-butylphenol), 4' -thiobis (3-methyl-6-tert-butylphenol) or Bis [3,3-Bis- (4 '-hydroxy-3' -t-butylphenyl) butanoic acid ] ethylene glycol ester; amine-based auxiliary antioxidants such as phenyl- α -naphthylamine, phenyl- β -naphthylamine, N '-diphenyl-p-phenylenediamine, or N, N' -di- β -naphthyl-p-phenylenediamine; a secondary sulfur antioxidant such as dilauryl disulfide, dilauryl thiopropionate, distearyl thiopropionate, mercaptobenzothiazole, or tetramethylthiuram disulfide, tetrakis [ methylene-3- (laurylthio) propionate ] methane; or phosphite-based auxiliary antioxidants such as triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecyl phosphite, bis (2, 4-dibutylphenyl) pentaerythritol diphosphite (Bis (2, 4-ditbutylphenyl) Pentaerythritol Diphosphit e), or tetrakis [2,4-Bis (1, 1-dimethylethyl) phenyl ] 4,4' -diyl biphosphonate ((1, 1' -Biphenyl) -4,4' -Diylbisphosphonous acid tetrakis [2,4-Bis (1, 1-di methyl yl) phenyl ] ester).
In one embodiment of the present specification, the antioxidant may be a hindered phenol-based antioxidant, and specifically, may be sonnox-1010 of pine origin.
As the ultraviolet absorber, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxybenzophenone, and the like can be used, but the ultraviolet absorber generally used in the art can be used without limitation thereto.
The thermal polymerization inhibitor may include, for example, 1 or more selected from the group consisting of anisole, hydroquinone, catechol (pyrocatechol), t-butyl catechol (t-butyl catechol), an ammonium salt of N-nitrosophenyl hydroxylamine, an aluminum salt of N-nitrosophenyl hydroxylamine, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, benzoquinone, 4-thiobis (3-methyl-6-t-butylphenol), 2-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptoimidazole, and phenothiazine (phenothiazine), but is not limited thereto, and a thermal polymerization inhibitor generally known in the art may be included.
The dispersant may be used by a method of adding the dispersant to the pigment in a form of surface-treating the pigment in advance, or a method of adding the dispersant to the pigment externally. The dispersant may be a compound type, nonionic, anionic or cationic dispersant, and examples thereof include fluorine type, ester type, cationic type, anionic type, nonionic type, and amphoteric type surfactants. These may be used individually or in combination of two or more.
Specifically, the dispersant is 1 or more selected from polyalkylene glycols and esters thereof, polyoxyalkylene polyols, ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, and alkylamines, but is not limited thereto.
The leveling agent may be polymerizable or non-polymerizable. Specific examples of the polymerizable leveling agent include polyethyleneimine, polyamide-amine, and reaction products of amine and epoxide, and specific examples of the non-polymerizable leveling agent include a non-polymerizable sulfur-containing compound and a non-polymerizable nitrogen-containing compound, but the present invention is not limited thereto, and leveling agents generally used in the art can be used.
According to an embodiment of the present specification, there is provided a photosensitive material produced using the photosensitive resin composition.
More specifically, the photosensitive resin composition described above in the present specification is applied to a substrate by a suitable method and cured to form a film or pattern-shaped photosensitive material.
The coating method is not particularly limited, and spray coating, roll coating, spin coating, or the like can be used, and spin coating is generally widely used. Further, after forming the coating film, a part of the residual solvent may be removed under reduced pressure, as the case may be.
As a light source for curing the photosensitive resin composition according to the present specification, for example, there are mercury vapor arc (arc), carbon arc, xe arc, and the like that emit light having a wavelength of 250nm to 450nm, but not limited thereto.
The photosensitive resin composition according to the present specification can be used for a pigment-dispersed photosensitive material for manufacturing a color filter of a thin film transistor liquid crystal display (TFT LCD), a photosensitive material for forming a black matrix of a thin film transistor liquid crystal display (TFT LCD) or an organic light emitting diode, a photosensitive material for forming an overcoat layer, a photosensitive material for a column spacer, a photocurable coating, a photocurable ink, a photocurable adhesive, a printing plate, a photosensitive material for a printed wiring board, a photosensitive material for a Plasma Display Panel (PDP), and the like, but the use thereof is not particularly limited.
According to an embodiment of the present specification, there is provided a color filter including the above photosensitive material.
The color filter can be produced using the photosensitive resin composition. Specifically, a color filter can be formed by applying the photosensitive resin composition to a substrate to form a coating film, exposing the coating film to light, developing, and curing.
The substrate may be a glass plate, a silicon wafer, a plate of a plastic base material such as polyether sulfone (PES), polycarbonate (PC), or the like, and the type thereof is not particularly limited.
The color filter may include a red pattern, a green pattern, a blue pattern, and a black matrix.
According to another embodiment, the above color filter may further comprise an overcoat layer.
For the purpose of improving contrast, a lattice-like black pattern called a black matrix may be arranged between color pixels of the color filter. As a material of the black matrix, chromium may be used. In this case, chromium may be vapor deposited on the entire glass substrate and patterned by etching. However, in view of high cost in the process, high reflectance of chromium, and environmental pollution caused by chromium waste liquid, a resin black matrix obtained by a pigment dispersion method that can be micromachined can be used.
A black matrix according to an embodiment of the present specification may use a black pigment or a black dye as a coloring material. For example, carbon black may be used alone or carbon black and a coloring pigment may be used in combination, and in this case, a coloring pigment having a poor light-shielding property is mixed, and therefore, there is an advantage that the strength of the film or the adhesion to the substrate is not lowered even if the amount of the coloring material is relatively increased.
An embodiment of the present specification provides a display device including the above color filter.
The display device may be any one of a plasma display panel (Plasma Display Panel, PDP), a light emitting diode (Light Emitting Diode, LED), an organic light emitting element (Organic Light Emitting Diode, OLED), a liquid crystal display device (Liquid Crystal Display, LCD), a thin film transistor liquid crystal display device (Thin FIlm Transistor-Liquid Crystal Display, LCD-TFT), and a Cathode Ray Tube (CRT).
Modes for carrying out the invention
In the following, examples are given to explain the present specification in detail. However, the embodiments according to the present specification may be modified into various forms, and the scope of the present specification is not to be construed as limited to the embodiments described below. The embodiments of the present description are provided to more fully explain the present description to those skilled in the art.
< example >
1. Synthetic examples of xanthene dyes
Synthesis example 1
To 30g of N-Methyl-2-Pyrrolidone (N-Methyl-2-pyrrosidone), 5g (12.34 mmol,1 eq.) of [ A ], 7.48g (61.692 mmol,5 eq.) of 2,6-dimethylaniline (2, 6-dimethyllaniline) were added and stirred while raising the temperature to 150 ℃. After reacting at 150℃for 4 hours, the mixture was cooled to room temperature, and 500mL of 1M aqueous HCl was slowly added. After the addition, the mixture was stirred for 1 hour, and the precipitate was filtered under reduced pressure. The filtrate was added to MeOH solvent and after refluxing (reflux) at 60 ℃ for 1 hour, filtration was performed under reduced pressure. Drying was performed in a Vacuum oven (Vacuum oven), whereby 3.07g of [ A-1] was obtained (yield 43.0%).
Ionization mode: APCI +: m/z=574 [ m+h ]] + Exact Mass): 574
2. Adhesive Synthesis examples
Synthesis example 2
51.75mol% of benzyl methacrylate, 8.63mol% of N-phenylmaleimide, 10.35mol% of styrene and 29.28mol% of methacrylic acid are added to a reaction vessel, mixed with a solvent, and heated to 60℃under a nitrogen atmosphere. Then, 10 parts by mass of a thermal polymerization initiator V65 (2, 3-azobis (2, 4-dimethylvaleronitrile)) was added based on the total weight of the binder resin solid content and reacted for 16 hours, thereby producing a binder resin a.
The acid value of the binder resin A thus produced was 125mgKOH/g, and the weight-average molecular weight was 8200. The binder resin a produced has the following structural units.
Synthesis example 3
In a reaction vessel, 17.71mol% methacrylic acid, 42.89mol% glycidyl methacrylate, and 39.40mol% styrene were added, mixed with a solvent and heated to 60 ℃ under nitrogen atmosphere. The binder resin B was produced by the same method as in synthetic example 2.
The acid value of the binder resin B thus produced was 85mgKOH/g, and the weight-average molecular weight was 8600. The binder resin B produced has the following structural units.
Synthesis example 4
A binder resin C was produced in the same manner as in Synthesis example 2 by adding 20.08mol% of methacrylic acid, 44.69mol% of styrene, and 35.23mol% of M100.
The acid value of the binder resin C thus produced was 95mgKOH/g, and the weight-average molecular weight was 8000. The binder resin C produced had the following structural units.
Synthesis example 5
37.57mol% of cyclohexyl methacrylate, 40.78mol% of glycidyl methacrylate, 21.24mol% of methacrylic acid, and 0.41mol% of diethylaminoethyl methacrylate were added, and the same procedure as in Synthesis example 2 was followed to prepare a binder resin D.
The acid value of the produced binder resin D was 92mgKOH/g, and the weight-average molecular weight was 6700. The produced binder resin D has the following structural units.
Synthesis example 6
39.22mol% of styrene, 42.58mol% of glycidyl methacrylate, 17.78mol% of methacrylic acid, and 0.42mol% of dimethylaminoethyl methacrylate were added to prepare a binder resin E by the same method as in Synthesis example 2.
The acid value of the produced binder resin E was 85mgKOH/g, and the weight-average molecular weight was 7600. The produced binder resin E has the following structural units.
Synthesis example 7
27.67mol% of cyclohexyl methacrylate, 39.70mol% of glycidyl methacrylate, 27.51mol% of methacrylic acid, and 5.12mol% of benzophenone methacrylate were added, and the same procedure as in Synthesis example 2 was followed to prepare a binder resin F.
The acid value of the produced binder resin F was 113mgKOH/g, and the weight-average molecular weight was 5900. The produced binder resin F has the following structural units.
Synthesis example 8
The binder resin G was produced by adding 27.19mol% of cyclohexyl methacrylate, 39.77mol% of glycidyl methacrylate, 27.50mol% of methacrylic acid, 5.13mol% of benzophenone methacrylate, and 0.41mol% of dimethylaminoethyl methacrylate, and the same procedure as in Synthesis example 2 was followed.
The acid value of the produced binder resin G was 99mgKOH/G, and the weight-average molecular weight was 28000. The produced binder resin G has the following structural units.
Synthesis example 9
The binder resin H was produced by adding 27.19mol% of cyclohexyl methacrylate, 39.77mol% of glycidyl methacrylate, 27.50mol% of methacrylic acid, 5.13mol% of benzophenone methacrylate, and 0.41mol% of diethylaminoethyl methacrylate, and producing the same manner as in synthetic example 2.
The acid value of the produced binder resin H was 106mgKOH/g, and the weight-average molecular weight was 6800. The produced binder resin H has the following structural units.
Synthesis example 10
The binder resin I was produced by adding 36.49mol% of styrene, 36.92mol% of cyclohexyl methacrylate, 18.80mol% of methacrylic acid, and 5.10mol% of benzophenone methacrylate and producing the same as in synthesis example 2.
The acid value of the produced binder resin I was 82mgKOH/g, and the weight-average molecular weight was 8500. The produced binder resin I has the following structural units.
[ production of photosensitive resin composition ]
Comparative example 1
The photosensitive resin composition of comparative example 1 was produced by mixing the compositions shown in table 1 below.
TABLE 1
[ production of photosensitive resin composition examples 1 to 10]
Photosensitive resin compositions of examples 1 to 10 were produced with the same components and contents as those described in table 1 except that the types and contents of binder resins were used as described in table 2 below.
TABLE 2
Adhesive resin Weight percent
Example 1 D 3.50
Example 2 E 3.50
Example 3 F 3.50
Example 4 G 3.50
Example 5 H 3.50
Example 6 I 3.50
Example 7 B+D 1.75+1.75
Example 8 C+F 1.75+1.75
Example 9 B+G 1.75+1.75
Example 10 C+I 1.75+1.75
< Experimental example >
[ production of substrate ]
The photosensitive resin compositions produced in examples 1 to 10 and comparative example 1 were spin-coated on glass (5 cm. Times.5 cm), and subjected to a pre-baking treatment at 110℃for 70 seconds to form a film. The film was exposed to a high pressure mercury lamp at 40mJ/cm using a photomask 2 The pattern was then developed with aqueous KOH base and washed with distilled water. After distilled water was removed, post-baking treatment was performed at 230 ℃ for 20 minutes, thereby obtaining a color pattern.
[ evaluation of Heat resistance ]
The post-baking treatment substrate manufactured under the above conditions was subjected to absorption spectrum in the wavelength range of 380 to 780nm by a spectrometer (MCPD, tsukamurella).
The post-baked treated substrate was further treated at 230℃for 120 minutes, and a transmittance spectrum was obtained in the same equipment and the same measurement range.
Values L, a, and b obtained from an absorption spectrum obtained by using a C light source as a backlight are used to calculate Δeab (heat resistance) by the following expression 1, and are shown in table 3 below.
[ calculation formula 1]
ΔEab(L*，a*，b*)＝{(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 } 1/2
A small Δeab value means a small color change, and thus excellent heat resistance.
[ evaluation of chemical resistance ]
After the substrate subjected to the post-baking treatment for 1 time was cut into 1cm×5cm, the absorption spectrum in the wavelength range of 380 to 780nm was measured by a spectrometer (MCPD, tsukamurella).
After the spectrum was obtained, it was immersed in 16g of N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone) solvent, and then, after being left at room temperature for 10 minutes, it was washed with distilled water. Transmittance spectra were obtained in the same apparatus and in the same measurement range.
The spectra before and after immersion were calculated by using the above-mentioned calculation formula 1, and Δeab (chemical resistance) is shown in the following table 3.
A small Δeab value means a small color change, and thus excellent chemical resistance.
TABLE 3
ΔEab (Heat resistance) ΔEab (chemical resistance)
Comparative example 1 4.75 5.83
Example 1 2.87 3.22
Example 2 2.54 2.97
Example 3 1.86 2.03
Example 4 1.48 1.28
Example 5 1.69 1.64
Example 6 2.16 1.10
Example 7 1.28 1.03
Example 8 1.19 0.98
Example 9 0.85 0.55
Example 10 2.21 1.85
From table 3 above, it was confirmed that the Δeab values of examples 1 to 10 are smaller than those of comparative example 1, and that color filters can be obtained by using the photosensitive resin compositions excellent in heat resistance and chemical resistance according to one embodiment of the present specification. Specifically, it was confirmed that the Δeab values of examples 4, 5 and 9, in which the structure represented by chemical formula 1 and the structure represented by chemical formula 2 were all contained, were small compared with the Δeab values of examples 1 and 2, in which the structure represented by chemical formula 2 was contained, and therefore, when the binder resin in which the structure represented by chemical formula 1 and the structure represented by chemical formula 2 were all contained, a photosensitive resin composition excellent in heat resistance and chemical resistance was used, and a color filter was obtained.

Claims (9)

1. A photosensitive resin composition comprising a xanthene dye represented by the following chemical formula 3, a binder resin containing one or more structures represented by the following chemical formulas 1 and/or 2, a polyfunctional monomer, a photoinitiator, and a solvent:
chemical formula 1
Chemical formula 2
In the chemical formulas 1 and 2 described above,
represents a moiety attached to other substituents or to a binding moiety,
x 'and X' are O or NH,
l1 to L4 and L3', which are identical to or different from each other, are each independently of one another directly bonded, alkylene having 1 to 30 carbon atoms, arylene having 6 to 30 carbon atoms, -C (=O) -, -L' -O (C=O) -, or-L '-O-L' -,
l ', L ' and L ' are the same or different from each other and each independently an alkylene group having 1 to 30 carbon atoms,
nx is-NH 2 Or an alkylamino group having 1 to 30 carbon atoms,
t1 to T4 are the same or different from each other and are each independently hydrogen, hydroxyl, or alkyl having 1 to 30 carbon atoms,
t2 is an integer of 0 to 4, and when T2 is 2 or more, T2 is the same or different from each other,
t3 is an integer of 0 to 5, and when T3 is 2 or more, T3 is the same or different from each other,
chemical formula 3
In the chemical formula 3 described above, the chemical formula,
r1 to R6 are the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a nitro group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms,
R7 to R11 are the same or different from each other and are each independently selected from hydrogen, deuterium, -OH, -SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COOH、-COO - Z + 、-COORa、-SO 3 Rb、-SO 2 NRcRd, -CONRe, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms,
Z + represents Na + Or K + ，
Ra and Rb are the same or different from each other and are each independently selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms,
rc to Re are the same or different from each other and are each independently selected from hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms,
rc and Rd optionally combine with each other to form a heterocyclic ring containing a nitrogen atom,
at least one of R7 to R11 is-SO 3 - 、-SO 3 H、-SO 3 - Z + 、-COO - 、-COO - Z + 、-COORa、-SO 3 Rb or-SO 2 NRcRd，
R12 to R15 are the same or different from each other and are each independently selected from hydrogen, deuterium, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms,
q1 and Q2 are the same or different from each other and each independently is a direct bond or an alkylene group having 1 to 30 carbon atoms,
rx is an anionic group or an ammonium structure,
a is 0 or 1.
2. The photosensitive resin composition according to claim 1, wherein the binder resin containing one or more structures represented by the chemical formulas 1 and/or 2 further contains a unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms.
3. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises a binder resin containing a unit derived from an unsaturated compound having a cyclic ether structure of 2 to 4 carbon atoms.
4. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises, based on the total weight of the photosensitive resin composition:
0.1 to 30 weight percent of the xanthene dye;
1 to 40% by weight of a binder resin containing one or more structures represented by the chemical formulas 1 and/or 2;
1 to 40 weight percent of a polyfunctional monomer;
0.1 to 10 wt% of a photoinitiator; and
the balance of solvent.
5. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the binder resin is 5000 to 30000g/mol.
6. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises one selected from a pigment and a dye other than the xanthene dye represented by the above chemical formula 3.
7. A photosensitive material produced using the photosensitive resin composition according to any one of claims 1 to 6.
8. A color filter comprising the photosensitive material of claim 7.
9. A display device comprising the color filter of claim 8.
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