Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/62—Quaternary ammonium compounds
  • C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D245/00—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms
  • C07D245/04—Heterocyclic compounds containing rings of more than seven members having two nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
  • C07D471/14—Ortho-condensed systems
• • 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
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
  • C09B62/62—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an ethylenimino or N—acylated ethylenimino group or a —CO—NH—CH2—CH2—X group, wherein X is a halogen atom, a quaternary ammonium group or O—acyl and acyl is derived from an organic or inorganic acid, or a beta—substituted ethylamine group
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—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

Definitions

• Novel compounds, core-shell dyes, photosensitive resin compositions and color filters comprising the same
• the present disclosure relates to a novel compound, a core-shell dye, a photosensitive resin composition comprising the same, and a color filter manufactured using the same.
• the liquid crystal display device which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent integration, and is widely used for notebook computers, monitors, and TV images.
• the liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and a ⁇ pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer, and an upper substrate on which a ⁇ pixel electrode is formed.
• the color filter comprises a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between pixels, and a plurality of colors, typically red (R), green (G), blue (B) to form each pixel.
• the pigment dispersion method which is a method of implementing a color filter, coats a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix, exposes a pattern of a form to be formed, and then removes a non-exposed portion with a solvent. It is a method in which a colored thin film is formed by repeating a series of processes of thermosetting.
• the coloring photosensitive resin composition used for manufacturing the color filter by the pigment dispersion method generally consists of alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, an epoxy resin, a solvent, other additives, etc.
• the pigment dispersion method is actively used to manufacture LCDs of mobile phones, notebook computers, monitors, TVs and the like.
• the photosensitive resin composition for color filters using a pigment dispersion method having various advantages, not only excellent pattern characteristics but also improved performance are required. Especially high color gamut In addition, the characteristics of high brightness and high contrast ratio are urgently required.
• the image sensor refers to a component of an image pickup device that generates an image from a mobile phone camera or a digital still camera (DSC).
• the image sensor is largely complementary to a solid-state charge coupled device (CCD) image sensor according to its manufacturing process and usage. It may be classified as a complementary metal oxide semiconductor (CMOS) image sensor.
• CMOS complementary metal oxide semiconductor
• the color image pickup device used in the solid-state image pickup device or the complementary metal oxide semiconductor includes a color filter having a filter segment of red, green, and blue addition and mixing primary colors on the light receiving device ( It is common to install color filters separately and to separate the colors. Recently, the size of a color filter mounted on such a color image pickup device is 2 ⁇ or less, which is 1/100 to 1/200 times that of a conventional color filter pattern for LCDs. Accordingly, the increase in resolution and the reduction of residues are important factors that determine the performance of the device.
• the color filter made of the pigment-type photosensitive resin composition there exists a brightness, contrast ratio, and limit derived from the pigment particle size.
• a smaller dispersion particle size is required for forming a fine pattern. Buung to these needs, by introducing a dye that does not form the particles instead of the pigment to prepare a "photosensitive resin composition suitable to the dye is an attempt to implement a color filter to improve the brightness and contrast ratio.
• the degradation of the luminance due to the deterioration of durability, such as light and heat resistance compared to the pigment is compared to the pigment.
• One embodiment is to provide novel compounds with excellent brightness and contrast ratio.
• Another embodiment is to provide a core-shell dye comprising the novel compound.
• Another embodiment is to provide a photosensitive resin composition comprising the novel compound or core-shell dye.
• Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.
• An embodiment provides a compound represented by the following formula (1).
• L 1 and L 2 are each independently a substituted or unsubstituted C1 to C20 alkylene group
• R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group,
• R 3 and R 4 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
• R 1 and R 2 may be each independently represented by the following Formula (2) or (3).
• A is a C3 to C20 cycloalkane ring or a benzene ring
• L 3 is a substituted or unsubstituted C1 to C10 alkylene group
• R 5 is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
• R 3 and R 4 are each independently substituted or unsubstituted C1 It may be a C6 to C20 aryl group unsubstituted or substituted with a CIO alkyl group or a CI to CIO alkyl group.
• the compound represented by Chemical Formula 1 may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-8.
• Another embodiment includes a core comprising a compound represented by Formula 1; And a shell surrounding the shell.
• the cell may be represented by the following Chemical Formula 4 or Chemical Formula 5.
• L a to L d are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.
• L a to L d may be each independently a substituted or unsubstituted C1 to C10 alkylene group.
• the cell may be represented by the following Chemical Formula 4-1 or Chemical Formula 5-1.
• the cage width of the shell may be 6.5 A to 5 A.
• the core may have a length of 1 nm to 3 nm.
• the core may have a maximum absorption peak at wavelengths of 530 nm to 680 nm.
• the core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21.
• the core-shell dye may comprise the core and the shell in a molar ratio of 1: 1.
• the core-shell dye may be a green dye.
• Another embodiment provides a photosensitive resin composition comprising the compound or the core-shell dye.
• the photosensitive resin composition may further include a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
• the photosensitive resin composition may further include a pigment.
• the photosensitive resin composition for a total amount of photosensitive resin composition, the compound or cores - 3 ⁇ 4 dye 0.5 0/0 to 10 parts by weight / 0;
• the binder resin 0.1 0/0 to 30 parts by weight 0 / .;
• the photopolymerizable monomer 0.1% by weight to 30 parts by weight 0/0; 0.1 wt% to 5 wt% of the photopolymerization initiator; and the balance of the solvent.
• the photosensitive resin composition may be malonic acid, 3-amino-1,2-propanediol, vinyl group, or
• a silane coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof containing a (meth) acryloxy group may be further included.
• Another embodiment provides a color filter manufactured using the photosensitive resin composition. And other specific details of the embodiments of the invention are included in the following description.
• FIG. 1 is a view showing the cage width (cage width) of the shell represented by the formula (5-1).
• At least one hydrogen atom of the compound "substituted" ' is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, Imino, azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, ester, ether, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or its Salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocyclo Alkyl group, C2 to C20
• Heterocycloalkenyl group "heterocycloalkynyl group”
• Heterocycloalkylene group means that at least one hetero atom of N , 0 , s or p is present in a ring compound of cycloalkyl, cycloalkenyl, cycloalkynyl and cycloalkylene, respectively. Unless stated otherwise in the present specification, "(meth) acrylate"
• L 1 and L 2 are each independently substituted or unsubstituted C1 to C20
• R 1 and R 2 are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
• R 3 and R 4 are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.
• the compound represented by Chemical Formula 1 may be used as a green dye as a compound having excellent green spectroscopic properties and high molar extinction coefficient. However, after the color resist is manufactured with an inferior durability compared to the pigment, a decrease in luminance may occur during the baking process.
• the compound according to one embodiment may have a substituent including a urethane linking group, thereby improving durability, and thus, having high brightness and high contrast ratio. Color filters can be implemented.
• R 1 and R 2 may be each independently represented by Formula 2 or Formula 3.
• A is a C3 to C20 cycloalkane ring or a benzene ring
• L 3 is a substituted or unsubstituted C1 to C10 alkylene group
• R 5 is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
• R 1 and R 2 may each independently be a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a C1 to C10 alkyl group including a substituted or unsubstituted acrylate group.
• the C3 to C10 cycloalkyl group may be a cyclopentyl group, a cyclonuclear group, a cycloheptyl group, and the like, but is not limited thereto.
• R 3 and R 4 may each independently be a substituted or unsubstituted C1 to C10 alkyl group or a C6 to C20 aryl group unsubstituted or substituted with a C1 to C10 alkyl group.
• solubility in a solvent to be described later may be 5 or more, such as 5 to 10.
• the solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent.
• the compound represented by Chemical Formula 1 may have excellent heat resistance.
• the pyrolysis temperature as measured by a thermogravimetric analyzer (TGA), may be at least 200 ° C, such as from 200 ° C to 300 ° C.
• the compound represented by Chemical Formula 1 has three resonance structures, as shown in the following scheme, but for the sake of convenience, the compound represented by Chemical Formula 1 may be represented by only one resonance structure. That is, the compound represented by Chemical Formula 1 may be represented by any one of three resonance structures.
• the compound represented by Chemical Formula 1 may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-8.
• Core-shell dye may have a structure consisting of a core and a shell surrounding the core.
• the core includes a compound represented by Chemical Formula 1.
• the shell may be a macrocyclic compound, the shell may form a coating layer surrounding the compound represented by the formula (1).
• the shell corresponding to the macrocyclic compound has a structure surrounding the compound represented by Chemical Formula 1, that is, the compound represented by Chemical Formula 1 exists inside the macrocyclic ring, It is possible to improve the durability of the core-shell dye, thereby realizing a high brightness and high contrast color filter.
• the compound included in the core or constituting the core is represented by Chemical Formula 1:
• the length of the compound may be 1 nm to 3 nm, such as 1.5 nm to 2 nm.
• a core-shell dye having a structure of a core and a shell surrounding the compound may be easily formed.
• the shell which is the macrocyclic compound, may be obtained in a structure surrounding the compound represented by Chemical Formula 1.
• Formula 1 contained in the core or constituting the core The compound represented may have a maximum absorption peak at wavelengths of 530 nm to 680 nm. Chemical formula having the above spectral characteristics .
• the core-shell dye which used the compound represented by 1 as a core as a green dye for example, the photosensitive resin composition for color filters which has high brightness and high contrast ratio can be obtained.
• the shell surrounding the core including the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 4 or Chemical Formula 5.
• L a to L d are each independently a single bond or a substituted or unsubstituted C1 to C10 halkylene group.
• L a to L d may be each independently a substituted or unsubstituted C1 to C10 alkylene group. In this case, it is excellent in solubility and it is easy to form the structure in which a shell surrounds the core containing the compound represented by the said Formula (1).
• the core-shell dye is a non-covalent bond, ie, a hydrogen bond, between an oxygen atom of a compound represented by Formula 1 and a hydrogen atom bonded to a nitrogen atom of a shell represented by Formula 4 or Formula 5 It may include.
• the shell may be represented by, for example, the formula 4-1 or 5-1.
• the cage width of the shell may be 6.5 A to 7.5 A, and the volume of the shell may be 10 A to 16 A.
• the cage width refers to a shell internal distance, such as a distance between two different phenylene groups in which a methylene group is connected to both sides in a shell represented by Formula 4-1 or Formula 5-1. (See Figure 1).
• the shell has a cage width within the above range, it is possible to obtain a core-shell dye having a structure surrounding the core containing the ash: compound represented by the formula (1), whereby the core-shell dye is a photosensitive resin
• the core-shell dye is a photosensitive resin
• the core-shell dye may include a core including the compound represented by Chemical Formula 1 and the shell in a molar ratio of 1: 1.
• a coating layer (shell) surrounding the core including the compound represented by Chemical Formula 1 may be well formed.
• the core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21, but is not limited thereto.
• the core-shell dye may be used alone as a green dye, or may be used in combination with a color dye.
• the dye examples include triaryl methane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azapopyrine dyes, indigo dyes, and xanthene dyes.
• the core-shell dyes may also be used in combination with pigments.
• a red pigment, a green pigment, a blue pigment, a yellow pigment, or a dark pigment may be used as the pigment.
• red pigment examples include CI. Red pigment 254, and the like can be mentioned CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270, CI Pigment Red 272, CI Pigment Red 177, CI Pigment Red '89.
• green pigment examples include CI green pigment 36, CI green pigment 7, I. green pigment 58 and the like.
• blue pigment examples include CI blue pigment 15: 6, CI blue pigment 15, CL blue pigment 15: 1, CI blue pigment 15: 2, CI blue pigment 15: 3, CI blue pigment 15: 4, CI blue pigment 15 Copper phthalocyanine pigments, such as: 5 and CL blue pigment 16, are mentioned.
• yellow pigment examples include isoindolin-based pigments such as CL yellow pigment 139, CI yellow pigment 138, and the like.
• Quinophthalone pigments C.I. Nickel complex pigments such as yellow pigment 150 and the like.
• Examples of the dark pigment include aniline black, perylene black, titanium black, carbon black and the like.
• the pigments may be used alone or in combination of two or more thereof, and are not limited to these examples.
• the pigment may be included in the photosensitive resin composition for color filters in the form of a dispersion.
• a pigment dispersion may be composed of the pigment, a solvent, a dispersant, a dispersion resin, and the like.
• the solvent may be ethylene glycol acetate, ethyl salosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol,
• Cyclonucanonone, propylene glycol methyl ether, and the like can be used, and among these, propylene glycol methyl ether acetate can be used.
• the dispersant helps to uniformly disperse the pigment in the dispersion, it can be used both nonionic, anionic or cationic dispersant.
• Alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkyl ' amide alkylene oxide adducts, alkyl amines and the like can be used, and these can be used alone or in combination of two or more thereof.
• the dispersion resin may use an acrylic resin including a carboxyl group, which may not only improve the stability of the pigment dispersion, but also improve the pattern of the pixel.
• the core-shell dye and the pigment When used in combination, they may be used in a weight ratio of 1: 9 to 9: 1, specifically, in a weight ratio of 3: 7 to 7: 3. When mixed in the weight ratio range, it may have a high brightness and contrast ratio while maintaining color characteristics.
• the compound represented by Formula 1 or the photosensitive resin composition comprising the core-shell dye is provided.
• the photosensitive resin composition comprises (A) a colorant - (compound of the formula (1), or the core-shell dyes), (B) a binder resin, (C) photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent It may include.
• the colorant may include the compound represented by Chemical Formula 1 and / or the core-shell dye, and the compound represented by Chemical Formula 1 and / or the core-shell dye has been described above.
• the colorant is a compound represented by Formula 1 and / or the core-shell
• the dye may further comprise a pigment, which has been described above.
• the formula compound and / or the core is represented by the first-shell dyes the color filter " ⁇ with respect to the photosensitive resin composition the total amount of 0.5 0/0 to 10% by weight," e.g. 0.5 0/0 to 5 parts by weight 0/0
• high luminance and contrast ratios may be expressed at a desired color coordinate.
• the binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.
• the first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof may include acrylic acid, methacrylic, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
• the first ethylenically unsaturated monomer may comprise from 5 parts by weight 0/0 to 50% by weight relative to the total amount of the alkali-soluble resin, for example 10% to 40% by weight.
• the C2-ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinylluene, and vinylbenzylmethyl ether; Methyl (meth) acrylate,
• Unsaturated carboxylic ester compounds such as benzyl (meth) acrylate, cyclonuclear chamber (meth) acrylate, and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compound of vinyl acetate, vinyl benzoate; Vinyl cyanide compounds such as unsaturated carboxylic acid glycidyl ester compound (meth) acrylonitrile such as glycidyl (meth) acrylate; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.
• binder resin examples include methacrylic acid / benzyl methacrylate Copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer,
• Methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but is not limited thereto. These may be used alone or in combination of two or more thereof.
• the weight average molecular weight of the binder resin may be 3,000 g / mol to 150,000 g / mol, such as 5,000 g / mol to 50,000 g / mol, such as 20,000 g / mol to 30,000 g / mol ⁇ the weight average molecular weight of the binder resin In the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.
• the acid value of the binder resin may be 15 mgKOH / g to 60 mgKOH / g, such as 20 mgKOH / g to 50 mgKOH / g. If the acid value of the binder resin is excellent in the above range, the resolution of the pixel can be obtained.
• the binder resin may be contained at 0.1 weight 0 /. To 30 parts by weight 0/0, for example 5% by weight to 20% by weight relative to the total photosensitive resin composition. In the case where the binder resin is included in the above range, the developability and the crosslinkability of the color filter may be improved to obtain excellent surface smoothness.
• a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.
• the photopolymerizable monomer may form a polymerized layer during exposure in the pattern forming process, thereby forming a pattern having excellent heat resistance, light resistance, and chemical resistance.
• 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-nucleic acid diol
• Di (meth) acrylate bisphenol A di (meth) acrylate, di (meth) acrylate, pentaerythritol, tri (meth) acrylate, pentaerythritol, tetra (meth) acrylate, penta Nutri (meta) acrylate, Dipentaerythritol di (meth) acrylate, dipentaerythritol
• Tri (meth) acrylate penta (meth) acrylate for dipentaerythr
• dipentaerythride is nucleated (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane
• Tri (meth) acrylate tris (meth) acryloyloxyethyl phosphate
• Examples of commercially available products of the photopolymerizable monomer are as follows.
• Examples of the monofunctional ester of (meth) acrylic acid include, but are not limited to, Aronix M-101 ®, M-1 1 1 ®, M-1 14 ® by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayak Co., Ltd. KAYARAD TC-1 1 OS®, TC-120S®, etc .; And V-158® and V-231 1 ® by Osaka Yuki Kagaku Kogyo Co., Ltd.
• Examples of the difunctional ester of (meth) acrylic acid include, but are not limited to, Aronix M-210®, M-240®, M-6200®, manufactured by Toagosei Kagaku Kogyo Co., Ltd .; KAYARAD HDDA® from Nihon Kayak Co., Ltd., HX-220® R-604®, etc .; The V-260®, V-312®, and V-335 HP® of Osaka Yuki Chemical Co., Ltd. are mentioned.
• Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309®, Copper M-400®, Copper M-405®, Copper M-450®, Copper, manufactured by Toagosei Chemical Industries, Ltd.
• the photopolymerizable monomer is to give better developability
• the photopolymerizable monomer may be included in the photosensitive resin composition with respect to the total amount of 0.1 0/0 to 30 parts by weight 0/0, for example 5 parts by weight 0 /. To 20 parts by weight 0 /.
• the photopolymerizable monomer When the photopolymerizable monomer is included in the above range, it is excellent in pattern characteristics and developability when manufacturing a color filter.
• photopolymerization initiator examples include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like. Can be used.
• Examples of the compounds of the acetophenone is, 2,2'-diethoxy particular when acetophenone, 2,2'-appendix when acetophenone, 2-hydroxy-_ _ _ 2-methyl propiophenone, 4-butyl-trichloro _
• Acetophenone, ⁇ -t-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2- Morpholino propane-1-one, 2-benzyl-2- dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.
• benzophenone compound examples include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.
• thioxanthone compound examples include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.
• benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.
• triazine-based compound examples include 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-lryl) -4,6-bis (trichloromethyl) -S-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -S-triazine ,
• Examples of the oxime compound include 2- ( 0 -benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, l- (o-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone; and the like.
• the photoinitiator is a carbazole compound, diketones in addition to the compound Compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds and the like can be used.
• the photomultiplier sum initiator may comprise from 0.1 weight 0/0 to 5 parts by weight 0/0, for example 1% by weight to 3 parts by weight 0/0 relative to the total photosensitive resin composition.
• the photopolymerization initiator is included within the above range hwaeteon for color filter manufacturing type:
• the solvent is not particularly limited, and specific examples thereof include alcohols such as methanol and ethane; Ethers such as dichloroethyl ether, n -butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, methyl ethyl carbye, diethyl carbye, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Carbyls such as glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates
• Acetic alkoxyalkyl esters such as acetates; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3- 3-alkoxypropionic acid alkyl esters such as ecoxypropionate; 2-hydroxy methoxy propionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionate alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-
• Ester compounds and also N-methylformamide, ⁇ , ⁇ -dimethylformamide, ⁇ -methylformanilide, ⁇ -methylacetamide, ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyridone, dimethyl Sulfoxide, benzyl ethyl ether, dinuclear ether, acetylacetone, isophorone, caproic acid : caprylic acid, 1-octanol, 1-nonane, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , ⁇ -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.
• glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diego .
• Diethylene glycols such as styrene glycol monomethyl ether;
• Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.
• These solvents may be included as part cup with respect to the total amount of photosensitive resin composition, specifically, may be incorporated into 20 parts by weight 0/0 to 90% by weight. When the solvent is included in the above range, the coating property of the photosensitive resin composition is excellent, the thickness
• the photosensitive resin composition may be used to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residues by undeveloped malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling crab; Fluorine-based surfactants; Additives, such as a radical polymerization initiator, may be further included.
• the photosensitive resin composition may further include an additive such as an epoxy compound in order to improve adhesiveness with a substrate.
• a phenol novolak epoxy compound a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.
• Another embodiment provides a "color filter manufactured by using the above-described photosensitive resin composition production method of the color filter is as follows.
• the above-mentioned photosensitive resin composition for color filters is applied at a thickness of 3.1 to 3.4 jwn, respectively, using a suitable method such as spin coating or slit coating. After application, light is irradiated to form a pattern required for the color filter. After irradiating with light, the coating layer is treated with an alkali developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of R, G and B colors, a color filter having a desired pattern can be obtained.
• crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.
• Triethylamine (15 mol) was added to dichloromethane and stirred for 24 hours. The solution was distilled under reduced pressure and separated by column chromatography to obtain Intermediate C-1ol.
• Synthesis Example 16 Synthesis with Intermediate C-2 Intermediate C-2 was obtained by the same method as Synthesis Example 2, except that Intermediate C-1 was used instead of Intermediate A-1.
• Synthesis Example 2 2 Synthesis of core-shell dye represented by Chemical Formula 1S Synthesis was carried out in the same manner as in Synthesis Example 21, except that Intermediate D-2 was used instead of Intermediate Dl to obtain a compound represented by Formula 15.
• Synthesis was carried out in the same manner as in Synthesis Example 21, except that 2-Isocyanatoethyl acrylatefi- was used instead of cyclohexyl isocyanate to obtain a compound represented by Chemical Formula 16.
• Phenyl isocyanate3 ⁇ 4- was used instead of cyclohexyl isocyanate, and was synthesized in the same manner as in Synthesis Example 21 to obtain a compound represented by Formula 20.
• Methacrylic acid / benzyl methacrylate copolymer having a weight average molecular weight of 22,000 g / m (combined weight ratio 15wt% / 85wt%)
• each component was mixed with the composition of following Tables 1-3, and the photosensitive resin composition was produced. Specifically, after dissolving the photopolymerization initiator in a solvent, the mixture is stirred at room temperature for 2 hours, and then stirred for 30 minutes by adding a dye (or pigment dispersion), and then adding a binder resin and a photopolymerizable monomer at room temperature for 2 hours. Stirred. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.
• the photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 4 was coated on a glass substrate having a thickness of imm degreasing washed, and 2 minutes on a 90 ° C. hot plate. Drying to give a coat. After exposure using a high pressure mercury lamp having a dominant wavelength of 365 nm in the coating film, After drying in an oven at 200 ° C for 20 minutes, the durability was confirmed by measuring the change in color coordinates using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), the results are shown in Table 4 below.
• Comparative Example 3 Good From Table 4, in the case of Examples 1 to 16 including the core-shell dye according to one embodiment, compared with the case of Comparative Examples 1 to 4 without the core-shell dye, durability It can be seen that this increased.
• Evaluation 2 Luminance and Contrast Rating
• the photosensitive resin composition prepared in Examples 1 to 16 and Comparative Examples 1 to 4 was applied on a glass substrate having a thickness of 1 mm by degreasing washing, and then dried on a 90 ° C. hot folate. Drying for minutes gave a coating. Subsequently, the coating film was exposed to light using a high pressure mercury lamp having a dominant wavelength of 365 nm, and then dried in a hot air circulation drying furnace at 200 ° C. for 5 minutes.
• the brightness and contrast ratio were measured using a spectrophotometer (MCPD3000, Otsuka electronic Co., Ltd.), and the results are shown in Table 5 below.
• Example 12 67.6 14500
• Example 13 67.3 15300
• the present invention is not limited to the above embodiments and may be manufactured in various other forms, and a person having ordinary knowledge in the art to which the present invention pertains may change the present invention without changing the technical spirit or essential features of the present invention. It will be appreciated that it may be implemented in a form. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

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