KR20130039949A - Photosensitive resin composition for color filter and color filter prepared by using the same - Google Patents
Photosensitive resin composition for color filter and color filter prepared by using the same Download PDFInfo
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- KR20130039949A KR20130039949A KR1020110104644A KR20110104644A KR20130039949A KR 20130039949 A KR20130039949 A KR 20130039949A KR 1020110104644 A KR1020110104644 A KR 1020110104644A KR 20110104644 A KR20110104644 A KR 20110104644A KR 20130039949 A KR20130039949 A KR 20130039949A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—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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- Optics & Photonics (AREA)
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- Engineering & Computer Science (AREA)
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- Materials For Photolithography (AREA)
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Abstract
The present invention relates to a photosensitive resin composition for color filters and a color filter manufactured using the same. Since the photosensitive resin composition for a color filter according to the present invention includes a dye having specific spectral characteristics together with a pigment, the color filter manufactured by using the same as well as having excellent light transmittance, brightness, contrast, and color purity, as well as improved heat resistance characteristics There is an advantage to represent.
Description
The present invention relates to a photosensitive resin composition for color filters and a color filter manufactured using the same.
Color filters are used in liquid crystal displays, organic light emitting devices, optical filters of cameras, and the like, and are generally manufactured by methods such as dyeing, printing, electrodeposition, and pigment dispersion.
Among them, the pigment dispersion method is the most common method of dispersing the pigment in the composition having photosensitivity in the wavelength region 200 ~ 400 nm to produce a color filter by a photolithography method.
This pigment dispersion method is stable to light, heat and the like by using the pigment, it is possible to manufacture a color filter in a relatively simple process. In addition, it is possible to adjust the brightness and contrast by lowering the particle size of the pigment and adjusting the degree of dispersion.
However, in the pigment dispersion method, when the content of the pigment is increased to improve the color purity, the luminance and contrast are inevitably lowered. This phenomenon has reached a limit that cannot be solved only by adjusting the particle size of the pigment. .
Accordingly, as a method for overcoming the limitation of the pigment dispersion method, a method of using a dye instead of a pigment has been proposed.
However, since the dye is basically poor solubility in a solvent, there is a limit to the amount available. Therefore, various methods for increasing the content of the dye have been proposed, such as improving the solubility of the dye. However, when the content of the dye is high, there is still a problem such that the dye precipitates after baking or the heat resistance decreases and thus the transmittance decreases. It is true.
Accordingly, the present invention is to provide a photosensitive resin composition capable of producing a color filter having excellent light transmittance, brightness, contrast, and color purity while showing improved heat resistance.
In addition, the present invention is to provide a color filter produced using the composition.
According to this embodiment of the present invention,
Binder resin; Reactive unsaturated compounds; Blue pigments; A dye having a spectral property of 90% or more in a wavelength range of 430 to 465 nm and a light transmittance of 55% or less in a wavelength range of 495 to 505 nm; A polymerization initiator; And the photosensitive resin composition for color filters containing a solvent is provided.
In addition, according to another embodiment of the present invention,
Binder resin; Reactive unsaturated compounds; Green pigments; A dye having a spectral property of 95% or more in a wavelength range of 530 to 540 nm and a light transmittance of 55% or less in a wavelength range of 580 to 590 nm; A polymerization initiator; And the photosensitive resin composition for color filters containing a solvent is provided.
In the composition according to the embodiments, the dye may be a compound represented by the following formula (1):
[Formula 1]
In Formula 1,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R 1 to R 16 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid alkyl group substituted with a sulfonic acid group, a heterocyclic group, a sulfonic acid hydroxy group, a sulfonic acid alkoxy group, a sulfonic acid aryl group, an alkyl group having 1 to 20 carbon atoms, and a carbon number 3 It is a cycloalkyl group of -20, a C6-C20 aryl group, a C1-C20 heteroalkyl group, a C3-C20 heterocycloalkyl group, or a C3-C20 heteroaryl group.
Preferably, the dye may be a compound represented by the following formula (2):
[Formula 2]
In Formula 2,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R a to R h are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, or a heterocycloalkyl group having 3 to 20 carbon atoms, or It is a C3-C20 heteroaryl group.
Also preferably, the dye having a spectral characteristic of 90% or more in the wavelength range of 430 to 465 nm and 55% or less in the wavelength range of 495 to 505 nm may include Octa (2-ethylhexyloxy) Cu Phthalocyanine, Octa (2-ethylhexyloxy ) Co Phthalocyanine, Octa (2-ethylhexyloxy) Al Phthalocyanine, Octa (2-ethylhexyloxy) Zn Phthalocyanine, Octa (2-ethylhexyloxy) Ni Phthalocyanine, Octa (2-ethylhexyloxy) Pt Phthalocyanine, and Octa (2-ethylhexyloxy) Cr Phthalocyanine It may be one or more compounds selected from the group consisting of.
In addition, preferably, the dye having a spectral characteristic of 95% or more transmittance in the
On the other hand, the photosensitive resin composition for color filters according to the embodiments
Per 100 parts by weight of the binder resin,
100 to 250 parts by weight of the reactive unsaturated compound;
5 to 150 parts by weight of the pigment;
50 to 250 parts by weight of the dye;
5 to 50 parts by weight of the polymerization initiator; And
100 to 500 parts by weight of the solvent
It may include.
Here, the binder resin is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, 2-acryloxyethylhydrogenphthalate, and 2-acrylooxypropylhydrogenphthalate. 10 to 40% by weight of the monomer having an ethylenic acid group; Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, ste (meth) arylacrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (Meth) acrylate, 2-hydroxyalkyl (meth) acrylate, trimethoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-acryloxyethyl2-hydroxypropyl (meth ) Phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, triethylsiloxaneethyl (meth) acrylate, and one or more kinds of (meth) acrylates selected from the group consisting of ethyltriglycol (meth)
In addition, the reactive unsaturated compound is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A (Meth) acrylate, trimethylolpropane tri (meth) acrylate, novolak epoxy (meth) acrylate, dipentaerythritol penta (meth) acrylate derivative having a carboxyl group, ethylene oxide glycerin trimethylolpropane tri (meth) Group consisting of acrylate, propylene oxide glycerin tri (meth) acrylate, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, thiol (meth) acrylate oligomer, and polyester (meth) acrylate oligomer It may be one or more compounds selected from.
On the other hand, according to another embodiment of the present invention, a color filter manufactured using the photosensitive resin composition is provided.
Since the photosensitive resin composition for a color filter according to the present invention includes a dye having specific spectral characteristics together with a pigment, the color filter manufactured by using the same as well as having excellent light transmittance, brightness, contrast, and color purity, as well as improved heat resistance characteristics There is an advantage to represent.
1A-1B and 2A-2B are graphs showing spectral characteristics for pigments and dyes that may be added to compositions according to embodiments of the invention.
3 and 4 are graphs showing the spectral characteristics of the color filters prepared using the compositions according to the embodiments and comparative examples of the present invention.
5A to 5B are enlarged photographs of an appearance of a color filter manufactured using a composition according to embodiments of the present invention.
Hereinafter, a photosensitive resin composition for a color filter and a color filter manufactured using the same according to embodiments of the present invention will be described.
Prior to this, some terms are defined as follows unless explicitly stated in the present specification and claims.
First, '(meth) acrylic acid' is defined as collectively referred to as acrylic acid and / or methacrylic acid.
In addition, "(meth) acrylate" is defined as collectively referred to as acrylate (acrylate) and / or methacrylate (methacrylate).
In addition, the "alkyl group" includes an alkyl group having 1 to 20 carbon atoms; "Cycloalkyl group" includes a cycloalkyl group having 3 to 20 carbon atoms; "Aryl group" includes an aryl group having 6 to 20 carbon atoms; 'Heteroalkyl group' includes a heteroalkyl group having 1 to 20 carbon atoms; "Heterocycloalkyl group" includes a heterocycloalkyl group having 3 to 20 carbon atoms; "Heteroaryl group" is defined as including a heteroaryl group having 3 to 20 carbon atoms. Here, "hetero" is defined as meaning that at least one carbon atom is substituted with an atom selected from the group consisting of O, S, N, P, Si or a combination thereof.
On the other hand, the present inventors in the process of studying the photosensitive resin composition for the color filter, when using a dye having a specific spectral characteristics with the pigment when the color exhibits excellent light transmittance, brightness, contrast, color purity and improved heat resistance characteristics It was confirmed that the filter can be produced, to complete the present invention.
According to one embodiment of the present invention, a binder resin; Reactive unsaturated compounds; Blue pigments; A dye having a spectral property of 90% or more in a wavelength range of 430 to 465 nm and a light transmittance of 55% or less in a wavelength range of 495 to 505 nm; A polymerization initiator; And the photosensitive resin composition for color filters containing a solvent is provided.
In addition, according to another embodiment of the present invention, a binder resin; Reactive unsaturated compounds; Green pigments; A dye having a spectral property of 95% or more in a wavelength range of 530 to 540 nm and a light transmittance of 55% or less in a wavelength range of 580 to 590 nm; A polymerization initiator; And the photosensitive resin composition for color filters containing a solvent is provided.
Hereinafter, each component that may be included in the photosensitive resin composition for color filters according to embodiments of the present invention will be described.
Binder resin
The binder resin is a component that ensures dispersion stability of pigments and dyes to be described later, and at the same time, a pixel having a desired resolution is formed during development.
Since the binder resin may be selected from binder resins generally used in resin compositions for color filters in the art, the configuration thereof is not particularly limited.
However, according to one embodiment of the present invention, the binder resin may be a copolymer in which a monomer having at least one ethylenic acid group and at least one (meth) acrylate monomer are polymerized.
In this case, the binder resin is 10 to 40% by weight monomer having an ethylene acid group and 60 to 90% by weight (meth) acrylate monomer, preferably 20 to 40% by weight monomer having an ethylene acid group and (meth)
That is, when the content of the monomer having an ethylenic acid group included in the binder resin is less than 10% by weight, solubility of the photosensitive resin composition in the alkaline developer may be reduced. In addition, when the content of the monomer having an ethylenic acid group included in the binder resin exceeds 40% by weight, dropping and tearing of the pattern may occur during development by an alkaline developer. In addition, when the content of the (meth) acrylate-based monomers included in the binder resin is less than 60% by weight, adhesion to the substrate is reduced during the development process, so that the pattern tearing phenomenon is severe and the straightness of the formed pattern is deteriorated. In addition, when the content of the (meth) acrylate-based monomers included in the binder resin exceeds 90% by weight, the time required for development may be long and productivity may decrease.
Here, the monomer having an ethylenic acid group is selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, 2-acryloxyethyl hydrogen phthalate, and 2-acryloxypropyl hydrogen phthalate. It may be one or more compounds.
In addition, the (meth) acrylate monomer is isobutyl (meth) acrylate, tert- butyl (meth) acrylate, lauryl (meth) acrylate, ste (meth) aryl acrylate, cyclohexyl (meth) acryl Latex, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyalkyl (meth) acrylate, trimethoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Acryloxyethyl2-hydroxypropyl (meth) phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, triethylsiloxaneethyl (meth) acrylate, and ethyltriglycol (meth) acrylate Selected from the group consisting of 1 It may be a more compounds.
In addition, the binder resin preferably has a weight average molecular weight (Mw) of 5,000 to 50,000 in consideration of adhesion to a substrate, dispersion stability of additional components, and the like.
Such binder resin may be included in 5 to 15% by weight based on the total weight of the composition. That is, in order to express the minimum dispersion stability, film strength, heat resistance, etc. according to the addition of the binder resin, the binder resin is preferably included in more than 5% by weight. In addition, when the binder resin is used in an excessive amount, the viscosity of the composition may be increased more than necessary, so that the optical properties, physical properties, and process efficiency of the composition may be lowered. In order to prevent such a phenomenon, the binder resin may be 15 wt% or less. It is preferable to be included as.
Reactive unsaturated compounds
On the other hand, the photosensitive resin composition for color filters which concerns on this invention contains a reactive unsaturated compound. The reactive unsaturated compound is a component for imparting viscosity to the composition and securing film strength together with the above-mentioned binder resin.
In particular, according to the present invention, the reactive unsaturated compound may be selected from the group consisting of a thermopolymerizable or photopolymerizable monomer, a thermopolymerizable or photopolymerizable oligomer and a mixture of two or more thereof.
Here, the thermally polymerizable or photopolymerizable monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, novolac epoxy (meth) acrylate, dipentaerythritol penta (meth) acrylate derivative having a carboxyl group, ethylene oxide glycerin trimethylolpropane tree It may be at least one compound selected from the group consisting of (meth) acrylate, and propylene oxide glycerine tri (meth) acrylate.
In addition, the thermally polymerizable or photopolymerizable oligomer is 1 selected from the group consisting of epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, thiol (meth) acrylate oligomer, and polyester (meth) acrylate oligomer. It may be a species or more oligomers.
Here, the content of the reactive unsaturated compound may be 100 to 250 parts by weight, preferably 150 to 250 parts by weight, more preferably 150 to 200 parts by weight based on 100 parts by weight of the binder resin. That is, in order to prevent the hardening of the pattern due to the low degree of curing of the photosensitive resin, the reactive unsaturated compound is preferably included 100 parts by weight or more based on 100 parts by weight of the binder resin. In addition, when the excess amount of the reactive unsaturated compound is added, the degree of cure of the composition becomes higher than necessary, thereby causing severe tearing of the pattern during development, and the linearity of the pattern may be lowered. It is preferable that it is contained below 250 weight part with respect to 100 weight part of binder resins.
Pigment
On the other hand, the photosensitive resin composition for color filters which concerns on this invention contains a pigment.
The pigment may be selected from blue or green pigments generally used in the colored resin composition for color filters in the art.
The blue pigment may be a copper phthalocyanine-based blue pigment, preferably a compound classified as a pigment in the color index, CI blue pigment (Color Index Pigment Blue) 15, 15: 3, 15: 4, 15 : 6, 60 etc. are mentioned.
In addition, the green pigment may be a halogenated phthalocyanine-based green pigment, preferably a compound classified as a pigment in the color index, it may be C.I. Green pigment (Color Index Pigment Green) 7, 36, 58 and the like.
Such pigments may be added directly to the composition according to the present invention as a pigment itself, or in the form of a pigment dispersion containing a dispersant or a solvent.
In this case, as the dispersant which may be included in the pigment dispersion, a nonionic dispersant, an ionic dispersant or a cationic dispersant may be selectively used, and specific examples thereof include polyalkylene glycol and esters thereof; Polyoxyalkylene; Polyhydric alcohol ester alkylene oxide adducts; Alcohol alkylene oxide adducts; Alkylamine etc. can be used individually or in combination suitably. The dispersant may be included in an amount of 10 to 20 parts by weight based on 100 parts by weight of the pigment.
In addition, as the solvent that may be included in the pigment dispersion composition, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like may be used. At this time, the content of the solvent is preferably adjusted so that the solid content of the pigment dispersion is 5 to 30% by weight.
On the other hand, the particle size of the pigment may be determined in consideration of dispersion stability and pixel resolution, and may be preferably a number average particle diameter of 30 to 200 nm.
The content of the pigment may be 50 to 150 parts by weight, preferably 75 to 150 parts by weight, and more preferably 75 to 125 parts by weight based on 100 parts by weight of the binder resin. That is, in consideration of color reproducibility, pattern shape, adhesiveness, curing properties, etc. according to the use of the pigment, the pigment is preferably included in the above-described range.
dyes
On the other hand, the photosensitive resin composition for color filters which concerns on this invention contains a dye.
In other words, the composition according to the present invention comprises the above-mentioned dye (secondary dye) together with the above-mentioned pigment (main pigment). According to the present invention, the dye has inherent spectral characteristics in a specific wavelength range, and the light transmittance and the light transmission width of the color filter formed by the composition are adjusted by synergy with the pigment showing a specific color, thereby improving color purity. Rather, the brightness, contrast and the like are improved.
Particularly, according to an embodiment of the present invention, when the pigment is a blue pigment, the dye represented by Chemical Formula 1 may have a light transmittance of 90% or more, preferably 90-99%, in the wavelength region of 430-465 nm, More preferably 93 to 99%; In the wavelength region 495 ~ 505 nm, the light transmittance may be a compound having a spectral characteristic of 55% or less, preferably 45 to 55%, more preferably 45 to 50%.
In addition, according to another embodiment of the present invention, when the pigment is a green pigment, the dye represented by the formula (1) is 95% or more, preferably 95 to 99% light transmittance in the wavelength range of 530 ~ 540 nm ; In the
Here, the pigment having the above spectral characteristics may be a compound represented by the following formula (1):
[Formula 1]
In Formula 1,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R 1 to R 16 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid alkyl group substituted with a sulfonic acid group, a heterocyclic group, a sulfonic acid hydroxy group, a sulfonic acid alkoxy group, a sulfonic acid aryl group, an alkyl group having 1 to 20 carbon atoms, and a carbon number 3 It is a cycloalkyl group of -20, a C6-C20 aryl group, a C1-C20 heteroalkyl group, a C3-C20 heterocycloalkyl group, or a C3-C20 heteroaryl group.
Preferably, the pigment having the spectral characteristics may be a compound represented by the following formula (2):
[Formula 2]
In Formula 2,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R a to R h are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, or a heterocycloalkyl group having 3 to 20 carbon atoms, or It is a C3-C20 heteroaryl group.
In this case, the compound represented by Chemical Formula 1 or Chemical Formula 2 may appear differently in blue or green color depending on the structure of R 1 to R 16 or R a to R h and the length of the substituent.
In particular, according to an embodiment of the present invention, blue dyes satisfying the spectral characteristics are Octa (2-ethylhexyloxy) Cu Phthalocyanine, Octa (2-ethylhexyloxy) Co Phthalocyanine, Octa (2-ethylhexyloxy) Al Phthalocyanine, Octa (2 -ethylhexyloxy) Zn Phthalocyanine, Octa (2-ethylhexyloxy) Ni Phthalocyanine, Octa (2-ethylhexyloxy) Pt Phthalocyanine, and Octa (2-ethylhexyloxy) Cr Phthalocyanine, but may be one or more compounds selected from the group consisting of The dye is not limited to these compounds.
In addition, according to an embodiment of the present invention, the green dye that satisfies the spectral characteristics are Octa (1,4,7,10-tetraoxaundecyl) Cu Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Co Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Al Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Zn Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Ni Phthalocyanine, Octa (1,4 , 7,10-tetraoxaundecyl) Pt Phthalocyanine, and Octa (1,4,7,10-tetraoxaundecyl) Cr Phthalocyanine may be one or more compounds selected from the group consisting of, but limiting the green dye to these compounds no.
The amount of the dye may be 50 to 250 parts by weight, preferably 100 to 250 parts by weight, and more preferably 100 to 200 parts by weight based on 100 parts by weight of the binder resin. That is, in order to express a minimum spectral synergistic effect according to the addition of the dye, the dye is preferably included at least 50 parts by weight based on 100 parts by weight of the binder resin. In addition, when the dye is used in excess, problems such as precipitation of the dye after baking or poor heat resistance may occur. In order to prevent such a phenomenon, the dye may be 200 parts by weight or less with respect to 100 parts by weight of the binder resin. It is preferred to be included.
polymerization Initiator
On the other hand, the photosensitive resin composition for color filters which concerns on this invention contains a polymerization initiator. The polymerization initiator is activated by heat or light or the like to induce the polymerization of the aforementioned reactive unsaturated compounds, and may be selected and used conventionally in the art.
However, according to one embodiment of the present invention, the polymerization initiator in the group consisting of acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds and mixtures thereof It may be selected.
Specifically, the polymerization initiator is 2,2'- diethoxy acetophenone, 2,2'-dibutoxy acetophenone, (2-hydroxy-2-methylethyl) phenyl ketone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 Acetophenone-based compounds including on-one and the like; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (diethyl amino) benzo Benzophenone compounds including phenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like; Thioxanthone, 2-Chrol Thioxanthone, 2-Methyl Thioxanthone, Isopropyl Thioxanthone, 2,4-Diethyl Thioxanthone, 2,4-Diisopropyl Thioxanthone, 2-Chloro Thioxide Thioxanthone type compound containing a santon etc .; Benzoin compounds including benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and the like; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloro methyl) -s-triazine, 2- (3 ', 4'-dimethoxy styryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piphenyl-4, 6-bis (trichloro methyl) -s-triazine, bis (trichloro methyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloro methyl ) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloro methyl (piperonyl)- Triazine-based compounds including 6-triazine, 2,4-trichloromethyl (4'-methoxy styryl) -6-triazine, and the like; 1,2-octadione-1- (4-phenylthio) phenol-2- (o-benzoyloxime) and ethanone-1- (9-ethyl) -6- (2-methylbenzoyl-3-yl)- Oxime compounds including 1- (o-acetyloxime) and the like and mixtures thereof.
In addition, a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, a biimidazole compound, or the like may be used as the polymerization initiator.
The content of the polymerization initiator may be determined in consideration of a phenomenon such as a decrease in transmittance due to the unreacted initiator after the polymerization reaction while sufficiently causing the polymerization reaction. According to the present invention, the content of the polymerization initiator may be 5 to 50 parts by weight, preferably 10 to 50 parts by weight, and more preferably 10 to 40 parts by weight based on 100 parts by weight of the binder resin.
solvent
On the other hand, the photosensitive resin composition for color filters which concerns on this invention contains a solvent.
The solvent is a component added to adjust the solubility and viscosity of the components included in the composition, and as long as it is compatible with the above components without showing reactivity, the conventional ones in the art can be used without limitation. have.
According to one embodiment of the invention, the solvent is alcohol, such as methanol, ethanol, isopropyl alcohol, butyl alcohol, benzyl alcohol diacetone alcohol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ethyl acetate, propylene glycol methyl ether acetate, and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate and the like; Or a mixture thereof.
In addition, the solvent is N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide Seed, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , Gamma-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, ethylene glycol acetate, ethyl cellosolve, ethyl lactate, polyethylene glycol and the like.
Preferably, in view of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether in the solvent; Cellosolve acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Ethylene glycol acetate, ethyl cellosolve, ethyl lactate, polyethylene glycol or mixtures thereof can be used.
The content of the solvent may be determined in consideration of the viscosity of the composition, the coating properties and the volatilization characteristics of the solvent. According to the present invention, the content of the solvent may be 100 to 500 parts by weight, preferably 150 to 450 parts by weight, more preferably 200 to 400 parts by weight based on 100 parts by weight of the binder resin.
Other additives
On the other hand, the photosensitive resin composition for color filters according to the present invention may further include other additives commonly used in the art, in addition to the above components.
The additive may mainly be a component for improving the storage stability of the composition or a component for improving the coating property and adhesion, and the like. According to the present invention, the additive may be an epoxy compound, malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a silicone or fluorine leveling agent, a surfactant, and the like. And, the content of these additives can be determined according to the physical properties to be adjusted within a range that does not adversely affect the physical properties of the composition, it is not particularly limited.
On the other hand, the present invention provides a color filter manufactured using the photosensitive resin composition described above, according to another embodiment.
The color filter may be manufactured by a conventional method in the art except for using the photosensitive resin composition according to the present invention.
According to one embodiment of the present invention, the color filter is applied to the above-mentioned photosensitive resin composition to a thickness of 1 to 5 ㎛ by a method such as spin coating or slit coating on a predetermined substrate, a predetermined pattern is formed here After irradiating light as much as possible, it may be prepared by treating it with a developing solution and performing a baking process as necessary to form a necessary pattern.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.
[ Manufacturing example ]
Manufacturing example One
(Manufacture of Binder Resin)
Polymerization initiator, based on 100 parts by weight of the monomer compound comprising 33% by weight of methacrylic acid, 40% by weight of benzyl methacrylate, 11% by weight of ethyltriglycol methacrylate, and 16% by weight of 2-hydroxyethylmethacrylate. 4 parts by weight of (azobisisobutyronitrile) and 55 parts by weight of a solvent (propylene glycol monoethyl ether) were mixed and polymerized to prepare a polymer resin having a weight average molecular weight of 30,000.
Manufacturing example 2-1
(Synthesis of blue dye: Octa (2-ethylhexyloxy) Cu Phthalocyanine)
About 12.8 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 7.0 g of copper cyanide were added to Dimethylformamide (about 130 ml), which was stirred at room temperature for about 5 hours under a nitrogen atmosphere. Thereafter, the solvent was removed under reduced pressure to obtain 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene.
Then, 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene (about 2 g), NH3 (about 2 g) and Na (about 0.34 g) are added to a methanol (about 34 ml) solvent, Stirring at room temperature for about 5 hours to obtain 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole.
The 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole (about 1.19 g) and Cu (about 0.2 g) were mixed and reacted for about 96 hours at a temperature of about 270 ° C., followed by Octa (2-ethylhexyloxy ) Cu Phthalocyanine was obtained.
Manufacturing example 2-2
(Synthesis of blue dye: Octa (2-ethylhexyloxy) Co Phthalocyanine)
About 12.8 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 7.0 g of copper cyanide were added to Dimethylformamide (about 130 ml), which was stirred at room temperature for about 5 hours under a nitrogen atmosphere. Thereafter, the solvent was removed under reduced pressure to obtain 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene.
Then, 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene (about 2 g), NH3 (about 2 g) and Na (about 0.34 g) are added to a methanol (about 34 ml) solvent, Stirring at room temperature for about 5 hours to obtain 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole.
The 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole (about 2 g) and Hydroquinone (about 0.215 g) were mixed and reacted for about 48 hours at a temperature of about 210 ° C., followed by Octa (2-ethylhexyloxy ) Dihydrogen Phthalocyanine was obtained.
Then, Octa (2-ethylhexyloxy) Dihydrogen Phthalocyanine (about 1.0 g) and CoCl 2 (about 0.363 g) were mixed and reacted at room temperature for about 24 hours to obtain Octa (2-ethylhexyloxy) Co Phthalocyanine.
Manufacturing example 2-3
(Synthesis of blue dye: Octa (2-ethylhexyloxy) Pt Phthalocyanine)
About 12.8 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 7.0 g of copper cyanide were added to Dimethylformamide (about 130 ml), which was stirred at room temperature for about 5 hours under a nitrogen atmosphere. Thereafter, the solvent was removed under reduced pressure to obtain 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene.
The 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene (about 2 g), NH 3 (about 2 g) and Na (about 0.34 g) were then added to a methanol (about 34 ml) solvent After stirring at room temperature for about 5 hours, 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole was obtained.
The 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole (about 1.5 g) and PtCl 2 (about 0.311 g) were mixed and reacted for about 48 hours at a temperature of about 270 ° C., thereby allowing Octa (2- ethylhexyloxy) Pt Phthalocyanine was obtained.
Manufacturing example 2-4
(Synthesis of blue dye: Octa (2-ethylhexyloxy) Dihydrogen Phthalocyanine)
About 12.8 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 7.0 g of copper cyanide were added to Dimethylformamide (about 130 ml), which was stirred at room temperature for about 5 hours under a nitrogen atmosphere. Thereafter, the solvent was removed under reduced pressure to obtain 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene.
The 1,2-Di (2-ethylhexyloxy) -4,5-dibromobenzene (about 2 g), NH 3 (about 2 g) and Na (about 0.34 g) were then added to a methanol (about 34 ml) solvent After stirring at room temperature for about 5 hours, 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole was obtained.
The 1,3-Diimino-5,6-di (2-ethylhexyloxy) isoindole (about 2 g) and Hydroquinone (about 0.215 g) were mixed and reacted for about 48 hours at a temperature of about 210 ° C., followed by Octa (2-ethylhexyloxy ) Dihydrogen Phthalocyanine was obtained.
Manufacturing example 3-1
(Synthesis of green dye: Octa (1,4,7,10-tetraoxaundecyl) Cu Phthalocyanine)
About 12.6 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 6.05 g of copper cyanide are added to the solvent Dimethylformamide (about 114 ml), which is about 15 hours under a nitrogen atmosphere and a temperature of 130 ° C. Was stirred. Then, the solvent was removed under reduced pressure to obtain 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene.
The 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene (about 3.55 g), NH 3 (about 2.0 g) and Na (about 0.39 g) were then added to methanol (about 39). ml) was added to the solvent and stirred at room temperature for about 5 hours to obtain 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole.
The 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole (about 1 g) and Cu (about 0.140 g) are mixed and reacted for about 18 hours at a temperature of about 220 ° C. To obtain Octa (1,4,7,10-tetraoxaundecyl) Cu Phthalocyanine.
Manufacturing example 3-2
(Synthesis of green dye: Octa (1,4,7,10-tetraoxaundecyl) Co Phthalocyanine)
About 12.6 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 6.05 g of copper cyanide are added to the solvent Dimethylformamide (about 114 ml), which is about 15 hours under a nitrogen atmosphere and a temperature of 130 ° C. Was stirred. Then, the solvent was removed under reduced pressure to obtain 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene.
The 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene (about 3.55 g), NH 3 (about 2.0 g) and Na (about 0.39 g) were then added to methanol (about 39). ml) was added to the solvent and stirred at room temperature for about 5 hours to obtain 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole.
The 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole (about 1.60 g) and Co (about 0.419 g) were mixed and reacted for about 17 hours at a temperature of about 280 ° C. To obtain Octa (1,4,7,10-tetraoxaundecyl) Co Phthalocyanine.
Manufacturing example 3-3
(Synthesis of green dye: Octa (1,4,7,10-tetraoxaundecyl) Pt Phthalocyanine)
About 12.6 g of 1,2-Di (2-ehtylhexyloxy) -4,5-dibromobenzene and about 6.05 g of copper cyanide are added to the solvent Dimethylformamide (about 114 ml), which is about 15 hours under a nitrogen atmosphere and a temperature of 130 ° C. Was stirred. Then, the solvent was removed under reduced pressure to obtain 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene.
The 1,2-Di (1,4,7,10-tetraoxaundecyl) -4,5-dicyanobenzene (about 3.55 g), NH 3 (about 2.0 g) and Na (about 0.39 g) were then added to methanol (about 39). ml) was added to the solvent and stirred at room temperature for about 5 hours to obtain 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole.
The 1,3-Diimino-5,6-di (1,4,7,10-tetraoxaundecyl) isoindole (about 1.5 g) and PtCl 2 (about 0.250 g) are added to Dimethylformamide (about 3.0 ml), which is room temperature. Was reacted for about 24 hours to obtain Octa (1,4,7,10-tetraoxaundecyl) Pt Phthalocyanine.
[ Example And Comparative example ]
Example One
Based on 100 parts by weight of the binder resin according to Preparation Example 1;
About 175 parts by weight of reactive unsaturated compound (ie, about 50 parts by weight of bisphenol epoxy acrylate oligomer and about 125 parts by weight of dipentaerythritol hexaacrylate);
About 625 parts by weight of a blue pigment dispersion (trade name: DJBLUE-01, manufactured by MIKYNI, solvent: propylene glycol methyl ether acetate, pigment 15% by weight, about 93.75 parts by weight of pigment);
About 28.75 parts by weight of the photopolymerization initiator (ie, about 6.25 parts by weight of OX-01 (manufacturer: BASF), about 15 parts by weight of Irgacure-369 (manufacturer: BASF), and about 4,4'-bisdiethylaminobenzophenone 7.5 parts by weight);
About 316.25 parts by weight of solvent propylene glycol methyl ether acetate; And
About 0.05 parts by weight of a fluorine-based leveling agent (trade name: F-474, manufacturer: DIC) were mixed, stirred at room temperature for about 2 hours, and impurities were removed through a 1.2 μm filtration filter.
Here, the dye according to Preparation Example 2-1 was mixed at about 125 parts by weight based on 100 parts by weight of the binder resin, and stirred at room temperature for 2 hours to prepare a photosensitive resin composition.
Example 2
In Example 1, a photosensitive resin composition was prepared under the same conditions and methods as in Example 1, except that the dye according to Preparation Example 2-2 was added in the same amount instead of the dye according to Preparation Example 2-1.
Example 3
In Example 1, the same conditions and methods as in Example 1 were used except that the dye according to Preparation Example 2-3 was added at about 100 parts by weight based on 100 parts by weight of the binder resin, instead of the dye according to Preparation Example 2-1. A photosensitive resin composition was prepared.
Comparative example One
In Example 1, a photosensitive resin composition was prepared under the same conditions and methods as in Example 1, except that the dye according to Preparation Example 2-1 was not added.
Comparative example 2
In Example 1, a photosensitive resin composition was prepared under the same conditions and methods as in Example 1, except that the dye according to Preparation Example 2-4 was added in the same amount instead of the dye according to Preparation Example 2-1.
Example 4
Based on 100 parts by weight of the binder resin according to Preparation Example 1;
About 175 parts by weight of reactive unsaturated compound (ie, about 50 parts by weight of bisphenol epoxy acrylate oligomer and about 125 parts by weight of dipentaerythritol hexaacrylate);
About 750 parts by weight of the green pigment dispersion (trade name: DJGREEN-01, manufacturer: special colorant, solvent: propylene glycol methyl ether acetate, pigment 15% by weight, about 112.5 parts by weight of pigment);
About 28.75 parts by weight of the photopolymerization initiator (ie, about 6.25 parts by weight of OX-01 (manufacturer: BASF), about 15 parts by weight of Irgacure-369 (manufacturer: BASF), and about 4,4'-bisdiethylaminobenzophenone 7.5 parts by weight);
About 316.25 parts by weight of solvent propylene glycol methyl ether acetate; And
About 0.05 parts by weight of a fluorine-based leveling agent (trade name: F-474, manufacturer: DIC) were mixed, stirred at room temperature for about 2 hours, and impurities were removed through a 1.2 μm filtration filter.
Here, the dye according to Preparation Example 3-1 was mixed at about 187.5 parts by weight based on 100 parts by weight of the binder resin, and stirred at room temperature for about 2 hours to prepare a photosensitive resin composition.
Example 5
In Example 4, except that the dye according to Preparation Example 3-2 was added in the same amount, instead of the dye according to Preparation Example 3-1, a photosensitive resin composition was prepared under the same conditions and methods as in Example 4.
Example 6
In Example 4, the same conditions and methods as in Example 4 were used except that the dye according to Preparation Example 3-3 was added at about 162.5 parts by weight based on 100 parts by weight of the binder resin, instead of the dye according to Preparation Example 3-1. A photosensitive resin composition was prepared.
Comparative example 3
In Example 4, a photosensitive resin composition was prepared under the same conditions and methods as in Example 4, except that the dye according to Preparation Example 3-1 was not added.
[ Experimental Example ]
Experimental Example One
(Measurement of Light Transmittance by Wavelength for Pigments and Dyes)
Blue pigment used in Examples 1 to 3 (FIG. 1A), dye according to Preparation Example 2-1, dyes (FIG. 1B) using Examples of chromaticity measurement equipment (manufacturer: Otsuka, model name: MCPD-3000) The spectral characteristics of the green pigment used in Fig. 6 (Fig. 2A) and the dye according to Preparation Example 3-1 (Fig. 2B) were measured, respectively, and the results are shown in Figs.
As can be seen from Figure 1b, the dye according to Preparation Example 2-1 has a spectral characteristic of more than about 90% of the transmittance in the wavelength region of 430 ~ 465 nm, less than about 55% of the transmittance in the wavelength range of 495 ~ 505 nm. Confirmed.
In addition, as can be seen through Figure 2b, the dye according to Preparation Example 3-1 has a spectral characteristic of more than about 95% of the transmittance in the wavelength range of 530 ~ 540 nm, and about 55% or less of the transmittance of about 55% in the wavelength range of 580 ~ 590 nm. It was confirmed to have.
Experimental Example 2
Each photosensitive resin composition according to the above examples and comparative examples was spin coated onto a glass substrate (10 × 10 cm) to a thickness of 2 μm, pre-bake for 2 minutes on a 90 ° C. hotplate. After the cooling, the mixture was cooled at room temperature for 1 minute. This was exposed using an exposure machine at an exposure dose of 100 mJ / cm 2 (365 nm standard), and then post-bake was performed for about 30 minutes in a ventilated oven at 220 ° C.
For each sample prepared by the above method, the spectral characteristics, light transmittance, brightness, contrast and heat resistance were measured by the following method, and the results are shown in Tables 1 to 2 and FIGS. 3 to 5.
(Measurement of light transmittance and wavelength appearance of each color region for color filter)
Using a chromaticity measurement equipment (manufacturer: Otsuka, model name: MCPD-3000), the color filter samples prepared by using the composition according to Example 2 and Comparative Example 1, and the composition according to Example 5 and Comparative Example 3 For each color filter sample prepared using the light transmittance for each wavelength region was measured by comparison, the results are shown in Figs.
In addition, the appearances of the color filter samples prepared by using the compositions according to Examples 2 and 5 were magnified and observed, and the results are shown in FIGS. 5A to 5B.
As can be seen from Figures 3 and 4, the sample prepared by using the composition according to the embodiments includes a dye that satisfies the intrinsic spectral characteristics in a specific wavelength range, by synergy with the pigment It was confirmed that the color purity was improved by adjusting the light transmittance and the light transmission width of the color filter.
(Transmittance measurement)
The light transmittance (%) was measured for the board | substrate after post-baking using MCPD-3000 apparatus (manufacturer: Otsuka). At this time, blue measured the maximum light transmittance (Max%) in the
(Luminance measurement)
The board | substrate after post-baking was measured for brightness | luminance (Y) using MCPD-3000 apparatus (Manufacturer: Otsuka). In this case, in order to compare the luminance based on a constant color coordinate, blue was measured under x: 0.14, y: 0.06, green for x: 0.25, and y: 0.63.
(Contrast measurement)
The substrate after the post-baking was measured using a CT-1 device (manufacturer: TSUBOSAKA) to measure the contrast according to the polarization. At this time, 30,000: 1 in the bare state was measured as a reference value.
(Heat resistance measurement)
The substrate after post-baking was heated in an oven at about 240 ° C. for about 30 minutes and then the color difference (ΔEab) was measured.
As can be seen from Table 1 and Table 2, the blue and green color filter samples prepared using the compositions according to Comparative Example 1 and Comparative Example 3 had a lower light transmittance and luminance than the Examples, It was confirmed that the contrast was relatively low due to the particle scattering effect.
In addition, the blue color filter prepared using the composition according to Comparative Example 2 was similar in the light transmittance, brightness, and contrast, but was poor in heat resistance and was found to be unsuitable for the liquid crystal display manufacturing process having an actual thermal process.
On the other hand, the color filter samples prepared using the compositions according to Examples 1 to 6 were excellent in transmittance, brightness and contrast, and were also confirmed to satisfy the reference value 3 or less required by the actual process in terms of heat resistance.
Claims (10)
Reactive unsaturated compounds;
Blue pigments;
A dye having a spectral property of 90% or more in a wavelength range of 430 to 465 nm and a light transmittance of 55% or less in a wavelength range of 495 to 505 nm;
A polymerization initiator; And
Photosensitive resin composition for color filters containing a solvent.
Reactive unsaturated compounds;
Green pigments;
A dye having a spectral property of 95% or more in a wavelength range of 530 to 540 nm and a light transmittance of 55% or less in a wavelength range of 580 to 590 nm;
A polymerization initiator; And
Photosensitive resin composition for color filters containing a solvent.
The dye is a photosensitive resin composition for a color filter is a compound represented by the following formula (1):
[Formula 1]
In Chemical Formula 1,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R 1 to R 16 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a sulfonic acid alkyl group substituted with a sulfonic acid group, a heterocyclic group, a sulfonic acid hydroxy group, a sulfonic acid alkoxy group, a sulfonic acid aryl group, an alkyl group having 1 to 20 carbon atoms, and a carbon number 3 It is a cycloalkyl group of -20, a C6-C20 aryl group, a C1-C20 heteroalkyl group, a C3-C20 heterocycloalkyl group, or a C3-C20 heteroaryl group.
The dye is a photosensitive resin composition for a color filter is a compound represented by the formula (2):
(2)
In Formula 2,
M is Cu, Co, Al, Zn, Ni, Pt or Cr;
R a to R h are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, or a heterocycloalkyl group having 3 to 20 carbon atoms, or It is a C3-C20 heteroaryl group.
The dyes include Octa (2-ethylhexyloxy) Cu Phthalocyanine, Octa (2-ethylhexyloxy) Co Phthalocyanine, Octa (2-ethylhexyloxy) Al Phthalocyanine, Octa (2-ethylhexyloxy) Zn Phthalocyanine, Octa (2-ethylhexyloxy) Ni Phthalocyanine, Octa ( A photosensitive resin composition for color filters, which is at least one compound selected from the group consisting of 2-ethylhexyloxy) Pt Phthalocyanine, and Octa (2-ethylhexyloxy) Cr Phthalocyanine.
The dye is Octa (1,4,7,10-tetraoxaundecyl) Cu Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Co Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Al Phthalocyanine, Octa 1,4,7,10-tetraoxaundecyl) Zn Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Ni Phthalocyanine, Octa (1,4,7,10-tetraoxaundecyl) Pt Phthalocyanine, and Octa (1,4, 7,10-tetraoxaundecyl) Photosensitive resin composition for color filters, which is at least one compound selected from the group consisting of Cr Phthalocyanine.
Per 100 parts by weight of the binder resin,
100 to 250 parts by weight of the reactive unsaturated compound;
5 to 150 parts by weight of the pigment;
50 to 250 parts by weight of the dye;
5 to 50 parts by weight of the polymerization initiator; And
100 to 500 parts by weight of the solvent
Wherein the photosensitive resin composition is a photosensitive resin composition for a color filter.
The binder resin is at least one ethylene-based selected from the group consisting of (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid, 2-acryloxyethylhydrogenphthalate, and 2-acryloxypropylhydrogenphthalate 10 to 40% by weight of the monomer having an acid group; Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, ste (meth) arylacrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (Meth) acrylate, 2-hydroxyalkyl (meth) acrylate, trimethoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-acryloxyethyl2-hydroxypropyl (meth ) At least one selected from the group consisting of phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, triethylsiloxaneethyl (meth) acrylate, and ethyltriglycol (meth) acrylate Acrylate Monomer 60 If a 90% by weight of a copolymer polymerized photosensitive resin composition for color filter.
The reactive unsaturated compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di ( Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A di (meth ) Acrylate, trimethylolpropane tri (meth) acrylate, novolac epoxy (meth) acrylate, dipentaerythritol penta (meth) acrylate derivative having a carboxyl group, ethylene oxide glycerin trimethylolpropane tri (meth) acrylate , Propylene oxide glycerin tri (meth) acrylate, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, thiol (meth) acrylate oligomer, and polyester (meth) acrylate oligomer The photosensitive resin composition for color filters which is 1 or more types of compounds which become.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110104644A KR101952252B1 (en) | 2011-10-13 | 2011-10-13 | Photosensitive resin composition for color filter and color filter prepared by using the same |
| PCT/KR2012/008316 WO2013055150A2 (en) | 2011-10-13 | 2012-10-12 | Photosensitive resin composition for color filter and color filter manufactured by using same |
| TW101137758A TW201321802A (en) | 2011-10-13 | 2012-10-12 | Photosensitive resin composition for color filter and color filter prepared by using the same |
| CN201280050041.0A CN103890658B (en) | 2011-10-13 | 2012-10-12 | Photosensitive resin composition for color filter and color filter made by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110104644A KR101952252B1 (en) | 2011-10-13 | 2011-10-13 | Photosensitive resin composition for color filter and color filter prepared by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130039949A true KR20130039949A (en) | 2013-04-23 |
| KR101952252B1 KR101952252B1 (en) | 2019-02-26 |
Family
ID=48082676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110104644A KR101952252B1 (en) | 2011-10-13 | 2011-10-13 | Photosensitive resin composition for color filter and color filter prepared by using the same |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101952252B1 (en) |
| CN (1) | CN103890658B (en) |
| TW (1) | TW201321802A (en) |
| WO (1) | WO2013055150A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9334399B2 (en) | 2012-12-12 | 2016-05-10 | Cheil Industries Inc. | Photosensitive resin composition and black spacer using the same |
| US9535190B2 (en) | 2014-01-09 | 2017-01-03 | Samsung Sdi Co., Ltd. | Photosensitive resin composition and color filter using the same |
| WO2018182135A1 (en) * | 2017-03-31 | 2018-10-04 | 동우 화인켐 주식회사 | Blue photosensitive resin composition, color filter produced by using same, and image display device |
| WO2021118042A1 (en) * | 2019-12-10 | 2021-06-17 | 극동제연공업 주식회사 | Colorant for heat transfer fluid, and composition comprising same |
| CN115003775A (en) * | 2019-11-04 | 2022-09-02 | Kd精细化工有限公司 | Colorants for heat transfer fluids and compositions containing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101750462B1 (en) | 2014-05-12 | 2017-06-23 | 제일모직 주식회사 | Novel compound, novel mixture, photosensitive resin composition, and color fliter |
| KR101819656B1 (en) | 2014-05-13 | 2018-01-17 | 제일모직 주식회사 | Photosensitive resin composition and color filter using the same |
| KR20170010969A (en) * | 2015-07-20 | 2017-02-02 | 이리도스 주식회사 | A colorant compound, and a colorant material comprising the same |
| CN110007561B (en) * | 2018-01-04 | 2022-07-19 | 东友精细化工有限公司 | Green photosensitive resin composition, color filter and image display device |
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| JP2002121412A (en) * | 2000-10-17 | 2002-04-23 | Nippon Shokubai Co Ltd | Copper phthalocyanin modified pigment and method of producing the same |
| JP2003161821A (en) * | 2000-12-22 | 2003-06-06 | Mitsubishi Chemicals Corp | Composition for color filter, and the color filter |
| JP2004157455A (en) * | 2002-11-08 | 2004-06-03 | Fuji Photo Film Co Ltd | Dye-containing hardening composition, color filter and its manufacturing method |
| JP2006058700A (en) * | 2004-08-20 | 2006-03-02 | Fuji Photo Film Co Ltd | Colored curable composition, color filter and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3707093B2 (en) * | 1995-04-28 | 2005-10-19 | 山本化成株式会社 | Phthalocyanine compound, intermediate thereof, method for producing the phthalocyanine compound, color filter using the same, and oil-based ink composition |
-
2011
- 2011-10-13 KR KR1020110104644A patent/KR101952252B1/en active IP Right Grant
-
2012
- 2012-10-12 CN CN201280050041.0A patent/CN103890658B/en active Active
- 2012-10-12 WO PCT/KR2012/008316 patent/WO2013055150A2/en active Application Filing
- 2012-10-12 TW TW101137758A patent/TW201321802A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002121412A (en) * | 2000-10-17 | 2002-04-23 | Nippon Shokubai Co Ltd | Copper phthalocyanin modified pigment and method of producing the same |
| JP2003161821A (en) * | 2000-12-22 | 2003-06-06 | Mitsubishi Chemicals Corp | Composition for color filter, and the color filter |
| JP2004157455A (en) * | 2002-11-08 | 2004-06-03 | Fuji Photo Film Co Ltd | Dye-containing hardening composition, color filter and its manufacturing method |
| JP2006058700A (en) * | 2004-08-20 | 2006-03-02 | Fuji Photo Film Co Ltd | Colored curable composition, color filter and method for producing same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9334399B2 (en) | 2012-12-12 | 2016-05-10 | Cheil Industries Inc. | Photosensitive resin composition and black spacer using the same |
| US9535190B2 (en) | 2014-01-09 | 2017-01-03 | Samsung Sdi Co., Ltd. | Photosensitive resin composition and color filter using the same |
| WO2018182135A1 (en) * | 2017-03-31 | 2018-10-04 | 동우 화인켐 주식회사 | Blue photosensitive resin composition, color filter produced by using same, and image display device |
| CN110446975A (en) * | 2017-03-31 | 2019-11-12 | 东友精细化工有限公司 | Blue-sensitive resin combination, the colour filter and image display device manufactured using it |
| CN115003775A (en) * | 2019-11-04 | 2022-09-02 | Kd精细化工有限公司 | Colorants for heat transfer fluids and compositions containing the same |
| CN115003775B (en) * | 2019-11-04 | 2024-03-19 | Kd精细化工有限公司 | Colorant for heat transfer fluid and composition containing same |
| WO2021118042A1 (en) * | 2019-12-10 | 2021-06-17 | 극동제연공업 주식회사 | Colorant for heat transfer fluid, and composition comprising same |
| KR20210144626A (en) * | 2019-12-10 | 2021-11-30 | 주식회사 케이디파인켐 | Colorants for Heat Transfer Fluids and Compositions Comprising the Same |
| EP4074781A4 (en) * | 2019-12-10 | 2023-12-20 | KD Finechem Co., Ltd. | Colorant for heat transfer fluid, and composition comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101952252B1 (en) | 2019-02-26 |
| WO2013055150A2 (en) | 2013-04-18 |
| TW201321802A (en) | 2013-06-01 |
| CN103890658A (en) | 2014-06-25 |
| WO2013055150A3 (en) | 2013-07-04 |
| CN103890658B (en) | 2017-12-05 |
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