WO2008078953A1 - Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same - Google Patents

Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same Download PDF

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Publication number
WO2008078953A1
WO2008078953A1 PCT/KR2007/006818 KR2007006818W WO2008078953A1 WO 2008078953 A1 WO2008078953 A1 WO 2008078953A1 KR 2007006818 W KR2007006818 W KR 2007006818W WO 2008078953 A1 WO2008078953 A1 WO 2008078953A1
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Prior art keywords
meth
acrylate
raven
black matrix
photoresist composition
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PCT/KR2007/006818
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French (fr)
Inventor
Dong-Chang Choi
Ho-Chan Ji
Geun-Young Cha
Dae-Hyun Kim
Kyung-Soo Choi
Han-Soo Kim
Sung-Hyun Kim
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Lg Chem, Ltd.
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Priority to JP2009543937A priority Critical patent/JP5329430B2/en
Priority to CN200780048485.XA priority patent/CN101573663B/en
Publication of WO2008078953A1 publication Critical patent/WO2008078953A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/08—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • 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
    • 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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a black matrix photoresist composition for a liquid crystal display and a black matrix prepared by using the same. More particularly, the present invention relates to a black matrix photoresist composition for a liquid crystal display, in which, while a wide process margin is ensured, photosensitivity is high and a pattern is stably formed with a small amount of exposure, thereby reducing a process time and improving a production yield, and an excellent light shielding characteristic is ensured to be easily applied to a large-scaled TV using a brighter backlight.
  • a black lattice pattern called a black matrix is generally disposed between color pixels of color filters.
  • Chromium is used in a black matrix according to the related art. In this process, chromium is deposited on an entire surface of a glass substrate and a pattern is formed through an etching process, which requires high costs and causes problems, such as high reflectivity of the chromium and environmental contamination due to wastewater with chromium. For this reason, various researches have been actively made on a resin black matrix using a pigment dispersion method in which minute processing can be performed.
  • the black matrix photoresist composition is prepared by mixing different colors of pigments or several kinds of pigments to have a black color. Since the photoresist composition serves to shield light, it contains a large amount of pigments that are not melt by a developing solution. For this reason, the black matrix photoresist composition has the following problems. A developing property is not good, a long time development is needed, or the resolution required cannot be obtained. Ac- cordingly, it has been required to improve a developing property in manufacturing a color filter of each color including a black matrix.
  • the black matrix photoresist composition needs to contain the coloring pigments with a high mixing ratio. As a result, viscosity of the composition increases, which makes it difficult to handle the composition or decreases strength of a formed film or adhesion of the film for a substrate.
  • Japanese Patent Application Publication No. 2005-156930 discloses a color filter composition that uses a binder newly developed for the purpose of improving sensitivity
  • Japanese Patent Application Publication No. 2005-338328 discloses a black resin composition whose sensitivity is improved by using a high-sensitive photopolymerization initiator
  • Japanese Patent Application Publication No. 2004-347916 discloses a black matrix composition whose sensitivity is improved by introducing a photopolymerization initiator and an organophosphorus compound.
  • an LCD Liquid Crystal Display
  • a region of an LCD field that concentrates on existing small and middle- sized mobile displays or monitors moves to a region of large-scaled monitors or TVs.
  • high sensitivity needs to be ensured to reduce a process time.
  • a backlight that has improved brightness has been adopted. As the brightness of the backlight increases, it has been required for a black matrix to have more excellent light shielding property than that in the related art.
  • the present inventors have discovered the fact that, when manufacturing a black matrix photoresist composition for a liquid crystal display, high sensitivity and a wide development margin can be ensured at the time of processing a black matrix by controlling an acid value and an unsaturated double bond ratio of a binder having a specific structure among components, and the obtained pattern has excellent characteristics.
  • the present invention provides a black matrix photoresist composition for a liquid crystal display that uses a binder having a specific structure where an acid value and an unsaturated double bond ratio are controlled, and a black matrix for a liquid crystal display that is prepared by using the black matrix photoresist composition for the liquid crystal display.
  • the present invention provides a liquid crystal display that includes the black matrix for the liquid crystal display.
  • the present invention provides a black matrix photoresist composition for a liquid crystal display, comprising, on the basis of 100 parts by weight of the black matrix photoresist composition, 1) 1 to 40 parts by weight of a coloring agent containing a black pigment; 2) 1 to 20 parts by weight of an alkali- soluble resin binder represented by the following Formula 1; 3) 1 to 20 parts by weight of a multifunctional monomer having an ethylenically unsaturated double bond; 4) 0.1 to 20 parts by weight of a photopolymerization initiator; and 5) 30 to 90 parts by weight of a solvent;
  • Rl indicates hydrogen, or a radical that forms an imide structure or a five-membered cyclic carboxylic anhydride together with X, for example, succinimide or succinic anhydride,
  • R2 is selected from the group consisting of hydrogen, methyl, and hydroxy methyl
  • R3 and R4 are the same or different from each other, and are independent hydrogen or methyl
  • X is selected from the group consisting of C to C alkyl esters, C to C alkyl esters substituted with 1 or 2 hydroxy groups, C to C alkyl esters substituted with C to C alkoxy groups, C to C alkyl esters substituted with halogen groups, C to C alkoxy
  • Y is selected from the group consisting of C to C alkylenes and C to C alkylene esters that include 1 to 10 ester groups
  • Z is selected from the group consisting of ethylene, propylene, butylene
  • a, b, c, and d indicate molar ratios of A, B, C, and D, respectively, and a is in a range of 10 to 90, b is in a range of 0 to 60, c is in a range of 0 to 40, and d is in a range of 0 to 40).
  • a, b, c, and d indicate molar ratios of A, B, C, and D, respectively, and a is in a range of 10 to 90, b is in a range of 0 to 60, c is in a range of 0 to 40, and d is in a range of 0 to 40).
  • the present invention provides a black matrix for a liquid crystal display that is manufactured by a manufacturing method comprising steps of:
  • the present invention provides a liquid crystal display comprising the black matrix for the liquid crystal display.
  • the black matrix for the liquid crystal display according to the present invention is advantageous in that a developing property, a light shielding property, and an insulating property are excellent, a residue does not exist, and defective display can be prevented from occurring due to heat treatment.
  • the black matrix when the black matrix is manufactured by controlling an acid value and an unsaturated double bond ratio of a binder having a specific structure, it is possible to perform a patterning process that is capable of realizing high optical density with a small amount of exposure, thereby forming a pattern having excellent straightness and film characteristics.
  • FIG. 1 is a graph illustrating a change in thickness of a photoresist compostion according to an embodiment of the present invention in response to an exposure.
  • FIG. 2 is a graph illustrating a change in pattern of a photoresist compostion according to an embodiment of the present invention in response to a development time.
  • the coloring agent containing the black pigment used in the present invention may be a mixture of carbon black and at least one coloring pigment.
  • Examples of carbon black comprise SEAST 5HIISAF-HS, SEAST KH, SEAST
  • 3HHAF-HS SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS, and SEAST SSRF (commercially available from Tokai Carbon Co., Ltd.); DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MAI l, OIL
  • Examples of a coloring pigment that can be mixed with the carbon black comprise
  • Carmine 6B (CI. 12490), Phthalocyanine Green (CI. 74260), Phthalocyanine Blue (CI. 74160), Mitsubishi Carbon Black MAlOO, Perylene Black (BASF K0084 and K0086), Cyanine Black, Lionol Yellow (CI. 21090), Lionol Yellow GRO (CI.21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI. 42595), CI. PIGMENT RED 97, 122, 149, 168, 177, 180, 192, 215; CL Pigment Green 7, 36; CL PIGMENT 15:1, 15:4, 15:6, 22, 60, 64; CI. PIGMENT 83, 139; and CL PIGMENT VIOLET 23.
  • a white pigment and a fluorescent pigment may be used.
  • the coloring pigment may be obtained by mixing one or more coloring pigments to have a black color.
  • the alkali- soluble resin binder represented by Formula 1, used in the present invention may comprise the following monomers.
  • monomers that are used to form the A portion may comprise at least one that is selected from unsaturated carboxylic acid esters, such as benzyl (meth) aery late, methyl(meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, ethylhexyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-chloropropy
  • Examples of monomers that are used to form the B portion in Formula 1 may comprise at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth)acryloyloxy)ethyl phthalate, mono- 2-((meth)acryloyloxy)ethyl succinate, and ⁇ -carboxy polycaprolactone mono(meth)acrylate.
  • the present invention is not limited thereto.
  • the C portion is formed as follows.
  • a monomer to form the A portion and a monomer to form the B portion are polymerized to prepare a polymer composed of the A portion and the B portion and the C portion derives from the B portion of the polymer.
  • a method of introducing the C portion into the polymer composed of the A portion and the B portion a method may be used in which an acid radical of the B portion and an epoxy radical of glycidyl(meth)acrylate are subjected to a ring-opening condensation reaction.
  • the condensation reaction may be performed by a method that can be easily recognized by those skilled in the art.
  • the D portion derives from the C portion of the polymer that is composed of the A, B, and C portions.
  • a method of introducing the D portion into the polymer that is composed of A, B, and C a method may be used in which a hydroxy radical of the C portion and a carboxylic anhydride are subjected to a ring- opening condensation reaction.
  • examples of an acid anhydride that may be used to introduce the D portion include succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, cis- 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, itaconic anhydride, trimellic anhydride, and cis-5-norbornene-endo-2,3-dicarboxylic anhydride.
  • succinic anhydride glutaric anhydride, adipic anhydride
  • phthalic anhydride hexahydrophthalic anhydride
  • cis- 1,2,3,6-tetrahydrophthalic anhydride 3,4,5,6-tetrahydrophthalic anhydride
  • itaconic anhydride trimellic anhydride
  • an acid value and an equivalent of an unsaturated double bond of the alkali- soluble resin binder represented by Formula 1 are as follows.
  • d is in a range of 0 to less than 5
  • an acid value of the alkali- soluble resin binder be in a range of approximately 50 to 150 KOH mg/g
  • an equivalent of an unsaturated double bond be in a range of 1000 to 2500
  • a sum between (acid valuexlO) and the equivalent of the unsaturated double bond be in a range of 1500 to 4000.
  • the acid value of the alkali-soluble resin binder be in a range of approximately 20 to 80 KOH mg/g
  • the equivalent of the unsaturated double bond be in a range of 400 to 1000
  • a sum between (acid valuexlO) and the equivalent of the unsaturated double bond be in a range of 500 to 1500.
  • the equivalent of the unsaturated double bond can be represented by Equation 1 given below.
  • the acid value of the alkali- soluble resin binder has 150 or more and the sum between (acid valuexlO) and the equivalent of the unsaturated double bond is less than 1500 wherein d is in a range of 0 to less than 5, the acid value is extremely high and thus a development margin is narrow. Further, the obtained pattern has excessive double bonds to be bad straightness, which makes it impossible to use the obtained pattern as a black matrix.
  • the sum between (acid valuexlO) and the equivalent of the unsaturated double bond is 4000 or more, due to bad sensitivity, a large amount of radiation is needed to form a pattern.
  • the acid value is 50 or less, development cannot be reliably performed, which makes it difficult to obtain a pattern. Further, a development time is lengthened and a process characteristic is deteriorated.
  • a weight average molecular weight of the alkali- soluble resin binder is preferably in a range of 1000 to 200000, and more preferably in a range of 5000 to 100000.
  • the alkali- soluble resin binder can be independently used. However, preferably, two or more kinds of alkali-soluble resin binders are mixed and used. Preferably, the alkali- soluble resin binder is contained in a range of 1 to 25 parts by weight based on the total weight of the photoresist composition. When the content of the alkali-soluble resin binder is less than 1 part by weight, adhesiveness of a formed film is lowered, and when the content thereof exceeds 25 parts by weight, strength and sensitivity of a formed image are lowered.
  • the multifunctional monomer that has an ethylentically unsaturated double bond used in the present invention, may use a compound that has at least one unsaturated radical, which is capable of being additionally polymerized with a boiling point of 100 0 C or more, or a functional monomer into which caprolactone is introduced.
  • the compound that has at least one unsaturated radical which is capable of being additionally polymerized with a boiling point of 100 0 C or more may be a mono- functional monomer, such as polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or phenoxyethyl(meth)acrylate; and a multifunctional monomer, such as polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acryatle, trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate.
  • a mono- functional monomer such as polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(me
  • the multifunctional monomer into which caprolactone is introduced may be any suitable monomer into which caprolactone is introduced.
  • the multifunctional monomer may be epoxyacrylate of bisphenol A derivatives, novolac-epoxyacrylate, and U-324A, U15HA, and U-4HA as urethane-based multifunctional acrylate.
  • the multifunctional monomer that has an ethylenically unsaturated double bond may be one monomer or a mixture of at least one two kinds of monomers.
  • the multifunctional monomer that has the ethylenically unsaturated double bond is contained in a range of 1 to 20 parts by weight (5 to 50 parts by weight on the basis of a solid a resin composition) based on the total weight of the photoresist composition.
  • the content of the multifunctional monomer is less than 1 part by weight, photosensitivity or strength of a coating film is lowered.
  • the content thereof exceeds 20 parts by weight, adhesiveness of the photosensitive resin layer is excessively strong, which causes problems in that strength of the coating film is insufficient and a pattern is lost at the time of development.
  • the photopolymerization initiator used in the present invention, is a material that generates a radical by light and initiates crosslinking, and is preferably obtained by mixing compounds of one or more kinds selected from the group consisting of ace- tophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds.
  • Examples of the acetophenone compounds that can be used as the photopolymerization initiator include 2-hydroxy-2-methyl-l-phenylpropan-l-on, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-on,
  • the triazine compounds include 3- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio ⁇ propionic acid,
  • oxime compounds include 1, 2-octadione,-l-(4-phenylthio)phenyl,-2-(o-benzoyloxime)(CGI-124 manufactured by Ciba-Geigy Corp.), and ethanon,- l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-, l-(o-acetyloxime) (CGI242).
  • the photopolymerization initiator is preferably used in a range of 1 to 300 parts by weight based on 100 parts by weight that corresponds to a sum between 3) the multifunctional monomer having an ethylenically unsaturated double bond and the unsaturated double bond included in a binder in a photoresist composition.
  • the photopolymerization initiator preferably uses 1 to 30 parts by weight of an ace- tophenone compound, 1 to 30 parts by weight of a biimidazole compound, 1 to 30 parts by weight of a triazin compound, and 1 to 30 parts by weight of an oxime compound.
  • the photopolymerization initiator may further contain 0.01 to 10 parts by weight of a photo crosslinking accelerator that accelerates generation of a radical as an auxiliary component, or 0.01 to 10 parts by weight of a hardener that accelerates hardening.
  • the photo crosslinking accelerator includes benzophenone compounds, such as benzophenone, 4,4-bis(dimethylamino)benzophenone,
  • the hardener may be 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole,
  • 2-mercaptobenzoxazole 2,5-dimercapto- 1 ,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol- tetrakis(3-mercaptopropionate), pentaerythritol-tris(3-mercaptopropionate), pen- taerythritol-tetrakis (2-mercaptoacetate) , pentaerythritol-tris (2-mercaptoacetate) , trimethylolpropane-tris(2-mercaptoacetate), or trimethylolpropane- tris (3 -mercaptopropionate) .
  • the solvent used in the present invention, may be propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanon, 2-heptanon, 3-heptanon, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl- 3-ethoxypropionate, ethyl-3-ethoxypropionate, butylacetate, amylpermate, isoamylacetate, isobutylacetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate, or ⁇ -butyrolacetate.
  • the solvent may be independently used
  • the photoresist composition that is used in the present invention may additionally use 6) a primary additive that is at least one selected from the group consisting of a dispersing agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, a thermal polymerization preventing agent, and a leveling agent.
  • a primary additive that is at least one selected from the group consisting of a dispersing agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, a thermal polymerization preventing agent, and a leveling agent.
  • the dispersing agent may be used by a method in which the dispersing agent is internally added to a pigment in a form of performing surface treatment on the pigment in advance, or a method in which the dispersing agent is externally added to the pigment.
  • the dispersing agent may be a polymeric dispersing agent, a nonionic dispersing agent, an anionic dispersing agent or a cationic dispersing agent.
  • dispersing agent may include polyalkyleneglycol and ester thereof, poly- oxyalkylene polyhydric alcohol, esteralkylene oxide additive, alcohol alkylene oxide additive, sulfonate ester, sulphonate, carboxylic ester, carboxylate, alkylami- dalkyleneoxide additive, and alkylamine. These materials may be independently added or added after mixing two or more kinds of materials.
  • the adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vin yl tris(2-methoxyethoxy)-silane, N- (2- aminoethyl) - 3 -aminopropylmethyldimethoxy silane, N-
  • 3-chloropropylmethyldimethoxysilane 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
  • antioxidant 2,2-thiobis(4-methyl-6-t-butylphenol), or 2,6-g,t-butylphenol may be used, and as the ultraviolet absorber,
  • the thermal polymerization preventing agent may be hydroquinone, p- methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2-methylene bis(4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.
  • the photoresist composition may further include 7) a secondary additive that is at least one selected from the group consisting of a carbon black dispersion, a resin binder having functionality, a monomer, a radiation-sensitive compound, and other additives.
  • the present invention provides a black matrix for a liquid crystal display that is manufactured according to a manufacturing method comprising steps of 1) applying a black matrix photoresist composition for a liquid crystal display according to the present invention to a panel; and 2) exposing and developing the applied black matrix photoresist composition.
  • the black matrix for the liquid crystal display is advantageous in that a developing property, a light shielding property, and an insulating property are excellent, a residue does not exist, and defective display can be prevented from occurring due to heat treatment.
  • the present invention provides a liquid crystal display that comprises the black matrix for the liquid crystal display.
  • the liquid crystal display can be manufactured using a general manufacturing method that can be easily recognized by those skilled in the art, except that the liquid crystal display comprises the black matrix for the liquid crystal display according to the present invention.
  • 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole 10 parts by weight of 4,4-bis(diethylamino)benzophenone, 5 parts by weight of mercaptobenzothiazole, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 1 part by weight of a leveling agent, 510 parts by weight of propylene glycol monomethyl ether acetate and 510 parts by weight of 3-methoxybutyl acetate as a solvent, are mixed. Then, the obtained mixture is stirred for 5 hours, so as to prepare a black matrix photoresist composition.
  • the photoresist composition solution prepared by the above-described method is spin-coated onto glass and prebaked at the temperature of about 100 0 C for 2 minutes, thereby forming a coating film having the thickness of approximately 1.29 ⁇ m. Then, the substrate is cooled down at the room temperature, and exposed with energy of 60 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 25 0 C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O 0 C for 30 minutes in a convection oven.
  • the thickness is 1.1 ⁇ m, the pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding property is obtained.
  • the photoresist composition obtained in EXAMPLE 1 is spin-coated onto glass and prebaked at the temperature of about 100 0 C for 2 minutes, thereby forming the coating film having the thickness of about 1.29 ⁇ m. Then, the substrate is cooled down at the room temperature, and exposed with the energy of 60 mJ/cm using the photomask under the high pressure mercury lamp. The exposed substrate is developed using the spray method in a KOH aqueous solution of 0.04% at the temperature of 25 0 C. At this time, while the development time is controlled in a range of 60 to 90 seconds, the process margin is tested. According to the experimental result, a line width rarely changes through the development time in a ragnge of 50 to 90 seconds, and stability in pattern is maintained (see FIG. 2).
  • 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole 10 parts by weight of 4,4-bis(diethylamino)benzophenone, 5 parts by weight of mercaptobenzothiazole, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion accelerator, 1 part by weight of a leveling agent, 510 parts by weight of propylene glycol monomethyl ether acetate and 510 parts by weight of 3-methoxybutyl acetateas a solvent, are mixed. Then, the obtained mixture is stirred for 5 hours, thereby manufacturing a black matrix photoresist composition.
  • the photoresist composition prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1.
  • the thickness is 1.1 ⁇ m
  • a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
  • the photoresist composition that is prepared using the above-described method is subjected to various processes in the same method as that of EXAMPLE 1.
  • the thickness is 1.1 ⁇ m
  • a pattern is not omitted
  • straightness is excellent
  • a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
  • a black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 4 uses 10 parts by weight of l,2-octadione,-l-(4-phenylthio)phenyl,-2-(o-benzoyloxime), 10 parts by weight of 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, and 5 parts by weight of mercaptobenzothiazole, as photopolymerization initiators.
  • the photoresist composition solution obtained in the above-described method is spin-coated onto alkali-free glass and prebaked at the temperature of about 100 0 C for 2 minutes, thereby forming a coating film having the thickness of about 1.3 ⁇ m. Then, the substrate is cooled down at the room temperature, and exposed with energy of 80 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 25 0 C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O 0 C for 30 minutes in a convection oven.
  • the photoresist composition solution that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1.
  • the thickness is 1.1 ⁇ m
  • a pattern is not omitted
  • straightness is excellent
  • a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
  • a black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 5 uses 30 parts by weight of 2-benzyl-2-(dimethylamino)-l-(4-morpholinophenyl)buthyl-l-on, 10 parts by weight of 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, and 5 parts by weight of mercaptobenzothiazole, as photopolymerization initiators.
  • the photoresist composition solution obtained in the above-described method is spin-coated onto alkali-free glass and prebaked at the temperature of about 100 0 C for 2 minutes, thereby forming a coating film having the thickness of about 1.37 ⁇ m. Then, the substrate is cooled down at the room temperature, and exposed with energy of 80 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 25 0 C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O 0 C for 30 minutes in a convection oven.
  • the photoresist composition solution that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1.
  • the thickness is 1.1 ⁇ m
  • a pattern is not omitted
  • straightness is excellent
  • a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
  • a black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 6 uses 60 parts by weight of a compound [molar ratio
  • the photoresist composition prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1.
  • the thickness is 1.1 ⁇ m, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion.
  • the optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
  • a black matrix photoresist composition having the same components as those in
  • a black matrix photoresist composition having the same components as those in
  • the photoresist composition that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1, and is then developed. As a result, a development time is too lengthened and thus it is difficult to obtain a pattern. Further, straightness of a developed pattern and a film characteristic are bad.
  • a black matrix photoresist composition having the same components as those in
  • the photoresist composition that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1, and is then developed. As a result, a development is fast and thus a pattern is omitted.

Abstract

The present invention relates to a black matrix photoresist composition for a liquid crystal display and a black matrix manufactured by using the same. In particular, in a photoresist composition that includes a coloring agent containing a black pigment, an alkali- soluble resin binder, a multifunctional monomer having an ethylenically unsaturated double bond, a pho- topolymerization initiator, and a solvent, a high-resolution pattern can be obtained by controlling a characteristic of a binder used, that is, a ratio of a reactive group and an acid value, and a margin with respect to a process characteristic is improved, and an excellent pattern characteristic is obtained without causing a pattern to be omitted or a residue to be generated.

Description

Description
BLACK MATRIX HIGH SENSITIVE PHOTORESIST
COMPOSITION FOR LIQUID CRYSTAL DISPLAY AND
BLACK MATRIX PREPARED BY USING THE SAME
Technical Field
[1] The present invention relates to a black matrix photoresist composition for a liquid crystal display and a black matrix prepared by using the same. More particularly, the present invention relates to a black matrix photoresist composition for a liquid crystal display, in which, while a wide process margin is ensured, photosensitivity is high and a pattern is stably formed with a small amount of exposure, thereby reducing a process time and improving a production yield, and an excellent light shielding characteristic is ensured to be easily applied to a large-scaled TV using a brighter backlight.
[2] This application claims priority benefits from Korean Patent Application No.
10-2006-133555, filed in the Korean Industrial Property Office on December 26, 2006, the entire content of which is fully incorporated herein by reference. Background Art
[3] In general, in patterns that are formed by using a photoresist composition containing a pigment, defects may easily occur due to development or water washing, and if pattern adhesion is improved, solubility of a non-image portion is deteriorated at the time of development and contamination may easily occur. This is caused because crosslinking density is low and photosensitivity is low, that is, a development margin is narrow at the time of forming a pattern through development.
[4] In order to improve contrast, a black lattice pattern called a black matrix is generally disposed between color pixels of color filters. Chromium is used in a black matrix according to the related art. In this process, chromium is deposited on an entire surface of a glass substrate and a pattern is formed through an etching process, which requires high costs and causes problems, such as high reflectivity of the chromium and environmental contamination due to wastewater with chromium. For this reason, various researches have been actively made on a resin black matrix using a pigment dispersion method in which minute processing can be performed.
[5] The black matrix photoresist composition is prepared by mixing different colors of pigments or several kinds of pigments to have a black color. Since the photoresist composition serves to shield light, it contains a large amount of pigments that are not melt by a developing solution. For this reason, the black matrix photoresist composition has the following problems. A developing property is not good, a long time development is needed, or the resolution required cannot be obtained. Ac- cordingly, it has been required to improve a developing property in manufacturing a color filter of each color including a black matrix.
[6] Although a research has been made on a method of preparing a black composition using coloring pigments other than carbon black, the coloring pigments other than the carbon black have a bad light shielding property. For this reason, the black matrix photoresist composition needs to contain the coloring pigments with a high mixing ratio. As a result, viscosity of the composition increases, which makes it difficult to handle the composition or decreases strength of a formed film or adhesion of the film for a substrate.
[7] Like this, a lot of researches need to be performed to form a black matrix photoresist composition for a liquid crystal display that has excellent tinting strength, coverness, and insulating property as well as a developing property. At present, the black matrix photoresist composition has been researched.
[8] Therefore, a lot of researches have been made on the photoresist composition, and the results are disclosed as follows. For example, Japanese Patent Application Publication No. 2005-156930 discloses a color filter composition that uses a binder newly developed for the purpose of improving sensitivity, and Japanese Patent Application Publication No. 2005-338328 discloses a black resin composition whose sensitivity is improved by using a high-sensitive photopolymerization initiator. Further, Japanese Patent Application Publication No. 2004-347916 discloses a black matrix composition whose sensitivity is improved by introducing a photopolymerization initiator and an organophosphorus compound. As other examples, Japanese Patent Application Publication Nos. 2005-215378, 2005-227797, 2005-275218, 2000-227654, 1999-326606, and 1999-143056, US Patent No. 5,866,298, and Korean Patent Application Publication Nos. 2006-0076413 and 2002-0031093 disclose the development of black matrixes.
[9] In recent years, an LCD (Liquid Crystal Display) plays a bigger role in a field of flat displays. A region of an LCD field that concentrates on existing small and middle- sized mobile displays or monitors moves to a region of large-scaled monitors or TVs. As a size of glass increases, high sensitivity needs to be ensured to reduce a process time. Since brightness needs to be improved due to an increase in size of a screen, a backlight that has improved brightness has been adopted. As the brightness of the backlight increases, it has been required for a black matrix to have more excellent light shielding property than that in the related art. Since a content of carbon black contained in a composition is increased in order to improve a light shielding property, a process characteristic of the black matrix has been deteriorated. Since the carbon black effectively absorbs ultraviolet rays as well as visible rays, it is difficult to transmit light to a lower end of a resist film at the time of radiating ultraviolet rays to form a pattern. As a result, it is difficult to harden the lower end, adhesion is deteriorated, and a T-top-typed pattern is formed in which a portion is removed or a lower portion is dented at the time of development. The amount of energy radiated is continuously decreased to reduce the process time, and thus it becomes difficult to ensure a stable pattern.
[10] Accordingly, a lot of researches need to be performed on a black matrix photoresist composition that has improved adhesion with a substrate, a wide development process margin, and improved photosensitivity. Disclosure of Invention Technical Problem
[11] In order to solve the above-described problems according to the related art, the present inventors have discovered the fact that, when manufacturing a black matrix photoresist composition for a liquid crystal display, high sensitivity and a wide development margin can be ensured at the time of processing a black matrix by controlling an acid value and an unsaturated double bond ratio of a binder having a specific structure among components, and the obtained pattern has excellent characteristics.
[12] The present invention provides a black matrix photoresist composition for a liquid crystal display that uses a binder having a specific structure where an acid value and an unsaturated double bond ratio are controlled, and a black matrix for a liquid crystal display that is prepared by using the black matrix photoresist composition for the liquid crystal display.
[13] Further, the present invention provides a liquid crystal display that includes the black matrix for the liquid crystal display. Technical Solution
[14] In order to achieve the above-described objects, the present invention provides a black matrix photoresist composition for a liquid crystal display, comprising, on the basis of 100 parts by weight of the black matrix photoresist composition, 1) 1 to 40 parts by weight of a coloring agent containing a black pigment; 2) 1 to 20 parts by weight of an alkali- soluble resin binder represented by the following Formula 1; 3) 1 to 20 parts by weight of a multifunctional monomer having an ethylenically unsaturated double bond; 4) 0.1 to 20 parts by weight of a photopolymerization initiator; and 5) 30 to 90 parts by weight of a solvent;
[15] [Formula 1]
[16]
Figure imgf000006_0001
[17] (wherein, Rl indicates hydrogen, or a radical that forms an imide structure or a five-membered cyclic carboxylic anhydride together with X, for example, succinimide or succinic anhydride,
[18] R2 is selected from the group consisting of hydrogen, methyl, and hydroxy methyl,
[19] R3 and R4 are the same or different from each other, and are independent hydrogen or methyl,
[20] X is selected from the group consisting of C to C alkyl esters, C to C alkyl esters substituted with 1 or 2 hydroxy groups, C to C alkyl esters substituted with C to C alkoxy groups, C to C alkyl esters substituted with halogen groups, C to C alkoxy
1 6 1 3 poly(n = 2 to 30) alkylenes, C and C glycol esters, C to C alkyl esters substituted
2 3 1 6 with phenyl groups, phenyl substituted with C 1 to C 6 alkyl groups, phenyl substituted with C 1 to C6 alkoxy groups, phenyl substituted with a halogen group, C 1 to C6 alkoxy methyl groups, glycidoxy methyl groups, and a radical that forms an imide structure or a five-membered cyclic carboxylic anhydride together with Rl, for example, maleimide or maleic anhydride, [21] Y is selected from the group consisting of C to C alkylenes and C to C alkylene esters that include 1 to 10 ester groups, [22] Z is selected from the group consisting of ethylene, propylene, butylene,
1 ,2-phenylene, 1 ,2-cyclohexylene,
Figure imgf000006_0002
[23] (where * indicates a connection portion), and
[24] a, b, c, and d indicate molar ratios of A, B, C, and D, respectively, and a is in a range of 10 to 90, b is in a range of 0 to 60, c is in a range of 0 to 40, and d is in a range of 0 to 40). [25] Further, the present invention provides a black matrix for a liquid crystal display that is manufactured by a manufacturing method comprising steps of:
[26] 1) applying the black matrix photoresist composition for the liquid crystal display according to the present invention to a panel; and
[27] 2) exposing and developing the applied black matrix photoresist composition.
[28] Furthermore, the present invention provides a liquid crystal display comprising the black matrix for the liquid crystal display.
Advantageous Effects
[29] The black matrix for the liquid crystal display according to the present invention is advantageous in that a developing property, a light shielding property, and an insulating property are excellent, a residue does not exist, and defective display can be prevented from occurring due to heat treatment.
[30] That is, in the present invention, when the black matrix is manufactured by controlling an acid value and an unsaturated double bond ratio of a binder having a specific structure, it is possible to perform a patterning process that is capable of realizing high optical density with a small amount of exposure, thereby forming a pattern having excellent straightness and film characteristics. Brief Description of the Drawings
[31] FIG. 1 is a graph illustrating a change in thickness of a photoresist compostion according to an embodiment of the present invention in response to an exposure.
[32] FIG. 2 is a graph illustrating a change in pattern of a photoresist compostion according to an embodiment of the present invention in response to a development time.
Best Mode for Carrying Out the Invention
[33] Hereinafter, the present invention will be described in detail by exemplifying a photoresist composition according to the present invention. However, it should be understood that the embodiments disclosed below are not limitative, but illustrative in all aspects.
[34] The coloring agent containing the black pigment used in the present invention may be a mixture of carbon black and at least one coloring pigment.
[35] Examples of carbon black comprise SEAST 5HIISAF-HS, SEAST KH, SEAST
3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS, and SEAST SSRF (commercially available from Tokai Carbon Co., Ltd.); DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MAI l, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B (commercially available from Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX- 140U, PRINTEX- 140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX- A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (commercially available from Degussa Japan Company); and RAVEN-1100ULTRA, RAVEN- 1080ULTRA, RAVEN- 1060ULTRA, RAVEN- 1040, RAVEN- 1035, RAVEN- 1020, RAVEN-1000, RAVEN- 890H, RAVEN-890, RAVEN-88OULTRA, RAVEN-860ULTRA, RAVEN- 850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN-2500ULTRA, RAVEN-2000, RAVEN- 1500, RAVEN- 1255, RAVEN- 1250, RAVEN- 1200, RAVEN- 1190ULTRA, and RAVEN- 1170 (commercially available from Columbia Carbon Co.).
[36] Examples of a coloring pigment that can be mixed with the carbon black comprise
Carmine 6B (CI. 12490), Phthalocyanine Green (CI. 74260), Phthalocyanine Blue (CI. 74160), Mitsubishi Carbon Black MAlOO, Perylene Black (BASF K0084 and K0086), Cyanine Black, Lionol Yellow (CI. 21090), Lionol Yellow GRO (CI.21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI. 42595), CI. PIGMENT RED 97, 122, 149, 168, 177, 180, 192, 215; CL Pigment Green 7, 36; CL PIGMENT 15:1, 15:4, 15:6, 22, 60, 64; CI. PIGMENT 83, 139; and CL PIGMENT VIOLET 23. In addition, a white pigment and a fluorescent pigment may be used. Further, the coloring pigment may be obtained by mixing one or more coloring pigments to have a black color.
[37] The alkali- soluble resin binder represented by Formula 1, used in the present invention, may comprise the following monomers. Examples of monomers that are used to form the A portion may comprise at least one that is selected from unsaturated carboxylic acid esters, such as benzyl (meth) aery late, methyl(meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, ethylhexyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-chloropropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, acyloctyloxy-2-hydroxypropyl(meth)acrylate, glycerol(meth)acrylate, 2-methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, ethoxydiethylene glycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, methoxytripropyleneglycol(meth)acrylate, poly(ethyleneglycol)methylether (meth)acrylate, phenoxydiethyleneglycol(meth)acrylate, p- nonylphenoxypolyethyleneglycol(meth)acrylate, p-nonylphenoxypolypropylene glycol(meth)acrylate, glycidyl(meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1 ,3,3,3-hexafluoroisopropyl(meth)acrylate, octafluoropentyl(meth)acrylate, hep- tadecafluorodecyl(meth)acrylate, tribromophenyl(meth)acrylate, dicyclopentanyl- methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethylacrylate, isobornylmethacrylate, adamantylmethacrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethylacrylate, and butyl α- hydroxymethylacrylate; aromatic vinyls, such as styrene, α-methylstyrene, (o,m,p)-vinyltoluene, (o,m,p)-methoxystyrene, and (o,m,p)-chlorostyrene; unsaturated ethers, such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; unsaturated imides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N- (4-hydroxyphenyl)maleimide, and N- cyclohexylmaleimide; and maleic anhydrides, such as maleic anhydride and methyl maleic anhydride. However, the present invention is not limited thereto.
[38] Examples of monomers that are used to form the B portion in Formula 1 may comprise at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth)acryloyloxy)ethyl phthalate, mono- 2-((meth)acryloyloxy)ethyl succinate, and ω-carboxy polycaprolactone mono(meth)acrylate. However, the present invention is not limited thereto.
[39] In Formula 1, the C portion is formed as follows. A monomer to form the A portion and a monomer to form the B portion are polymerized to prepare a polymer composed of the A portion and the B portion and the C portion derives from the B portion of the polymer. As a method of introducing the C portion into the polymer composed of the A portion and the B portion, a method may be used in which an acid radical of the B portion and an epoxy radical of glycidyl(meth)acrylate are subjected to a ring-opening condensation reaction. The condensation reaction may be performed by a method that can be easily recognized by those skilled in the art.
[40] Further, in Formula 1, the D portion derives from the C portion of the polymer that is composed of the A, B, and C portions. As a method of introducing the D portion into the polymer that is composed of A, B, and C, a method may be used in which a hydroxy radical of the C portion and a carboxylic anhydride are subjected to a ring- opening condensation reaction. Specifically, examples of an acid anhydride that may be used to introduce the D portion include succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, cis- 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, itaconic anhydride, trimellic anhydride, and cis-5-norbornene-endo-2,3-dicarboxylic anhydride. However, the present invention is not limited thereto.
[41] In the alkali- soluble resin binder represented by Formula 1 used in the present invention, when d is in a range of 0 to less than 5, b is in a rang of 5 to 60, and when d is in a range of 5 to 40, b is in a range of 0 to 10.
[42] Further, an acid value and an equivalent of an unsaturated double bond of the alkali- soluble resin binder represented by Formula 1 are as follows. When d is in a range of 0 to less than 5, it is preferable that an acid value of the alkali- soluble resin binder be in a range of approximately 50 to 150 KOH mg/g, an equivalent of an unsaturated double bond be in a range of 1000 to 2500, and a sum between (acid valuexlO) and the equivalent of the unsaturated double bond be in a range of 1500 to 4000. When d is in a range of 5 to 40, it is preferable that the acid value of the alkali-soluble resin binder be in a range of approximately 20 to 80 KOH mg/g, the equivalent of the unsaturated double bond be in a range of 400 to 1000, and a sum between (acid valuexlO) and the equivalent of the unsaturated double bond be in a range of 500 to 1500. Here, the equivalent of the unsaturated double bond can be represented by Equation 1 given below.
[43] [Equation 1]
[44] Equivalent of double bond = (molecular weight in repetitive unit)/(number of double bonds in repetitive unit)
[45] Assuming that the acid value of the alkali-soluble resin binder is P(KOH mg/g) and the equivalent of the double bond is Q, the conditions 50 <P < 150, 1000 <Q <2500, and 1500 ( (10xP)+Q ^ 4000 are satisfied when d is in a range of 0 to less than 5, and the conditions 20 <P < 80, 400 <Q < 1000, and 500 < (10xP)+Q < 1500 are satisfied when d is in a range of 5 to 40, so as to realize high sensitivity and high optical density.
[46] When the acid value of the alkali- soluble resin binder has 150 or more and the sum between (acid valuexlO) and the equivalent of the unsaturated double bond is less than 1500 wherein d is in a range of 0 to less than 5, the acid value is extremely high and thus a development margin is narrow. Further, the obtained pattern has excessive double bonds to be bad straightness, which makes it impossible to use the obtained pattern as a black matrix. When the sum between (acid valuexlO) and the equivalent of the unsaturated double bond is 4000 or more, due to bad sensitivity, a large amount of radiation is needed to form a pattern. Further, when the acid value is 50 or less, development cannot be reliably performed, which makes it difficult to obtain a pattern. Further, a development time is lengthened and a process characteristic is deteriorated.
[47] When d is in a range of 5 to 40, a carboxylic acid group that can be developed by an alkali development solution does not exist on a main chain and protrudes to a branched chain. Therefore, even though an acid value is small, a developing property is excellent. When the acid value is 80 or more, overdevelopment may easily occur, a pattern may be easily omitted, and it becomes difficult to realize high sensitivity.
[48] A weight average molecular weight of the alkali- soluble resin binder is preferably in a range of 1000 to 200000, and more preferably in a range of 5000 to 100000.
[49] The alkali- soluble resin binder can be independently used. However, preferably, two or more kinds of alkali-soluble resin binders are mixed and used. Preferably, the alkali- soluble resin binder is contained in a range of 1 to 25 parts by weight based on the total weight of the photoresist composition. When the content of the alkali-soluble resin binder is less than 1 part by weight, adhesiveness of a formed film is lowered, and when the content thereof exceeds 25 parts by weight, strength and sensitivity of a formed image are lowered.
[50] The multifunctional monomer that has an ethylentically unsaturated double bond, used in the present invention, may use a compound that has at least one unsaturated radical, which is capable of being additionally polymerized with a boiling point of 1000C or more, or a functional monomer into which caprolactone is introduced.
[51] The compound that has at least one unsaturated radical, which is capable of being additionally polymerized with a boiling point of 1000C or more may be a mono- functional monomer, such as polyethylene glycolmono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or phenoxyethyl(meth)acrylate; and a multifunctional monomer, such as polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acryatle, trimethylol ethane triacrylate, trimethylol propane triacrylate, neopentyl glycol (meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate.
[52] Further, the multifunctional monomer into which caprolactone is introduced may be
KAYARAD DPCA-20, 30, 60, 120 introduced into dipentaerythritol, KAYARAD TC- HOS introduced into tetrahydrofuryl acrylate, or KAYARAD HX-220 and KAYARAD HK-620 introduced into neopentylglycol hydroxypivalate. In addition to the above-described examples, the multifunctional monomer may be epoxyacrylate of bisphenol A derivatives, novolac-epoxyacrylate, and U-324A, U15HA, and U-4HA as urethane-based multifunctional acrylate.
[53] The multifunctional monomer that has an ethylenically unsaturated double bond may be one monomer or a mixture of at least one two kinds of monomers.
[54] Preferably, the multifunctional monomer that has the ethylenically unsaturated double bond is contained in a range of 1 to 20 parts by weight (5 to 50 parts by weight on the basis of a solid a resin composition) based on the total weight of the photoresist composition. When the content of the multifunctional monomer is less than 1 part by weight, photosensitivity or strength of a coating film is lowered. When the content thereof exceeds 20 parts by weight, adhesiveness of the photosensitive resin layer is excessively strong, which causes problems in that strength of the coating film is insufficient and a pattern is lost at the time of development.
[55] The photopolymerization initiator, used in the present invention, is a material that generates a radical by light and initiates crosslinking, and is preferably obtained by mixing compounds of one or more kinds selected from the group consisting of ace- tophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds.
[56] Examples of the acetophenone compounds that can be used as the photopolymerization initiator include 2-hydroxy-2-methyl-l-phenylpropan-l-on, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-on,
4- (2-hydroxyethoxy)-phenyl- (2-hydroxy-2-propyl)ketone, 1 -hydroxy cyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobuthyl ether, benzoin butyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-(4-methylthio)phenyl-2-morpholino- 1 -propan- 1 -on, 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butan-l-on, 2-(4-bromo-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butan-l-on, and 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinopropane-l-on. Examples of the biimidazole compounds include 2,2-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl biimidazole,
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4,5-trimethoxyphenyl)-l,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyl biimidazole, and 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-l,2'-biimidazole. Examples of the triazine compounds include 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl] phenylthio} propionic acid,
1,1,1 ,3,3,3-hexafluoroisopropyl-3- {4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthi o jpropionate, ethyl-2- { 4- [2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio } acetate, 2-epoxyethyl-2- { 4- [2,4-bis (trichloromethyl)-s-triazin-6-yl]phenylthio } acetate, cyclohexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl- 2- { 4- [2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio } acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazin,
2,4-bis(trichloromethyl)-6-(l-p-dimethylaminophenyl)-l,3,-butadienyl-s-triazin, and 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazin. Examples of the oxime compounds include 1, 2-octadione,-l-(4-phenylthio)phenyl,-2-(o-benzoyloxime)(CGI-124 manufactured by Ciba-Geigy Corp.), and ethanon,- l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-, l-(o-acetyloxime) (CGI242).
[57] The photopolymerization initiator is preferably used in a range of 1 to 300 parts by weight based on 100 parts by weight that corresponds to a sum between 3) the multifunctional monomer having an ethylenically unsaturated double bond and the unsaturated double bond included in a binder in a photoresist composition. In particular, the photopolymerization initiator preferably uses 1 to 30 parts by weight of an ace- tophenone compound, 1 to 30 parts by weight of a biimidazole compound, 1 to 30 parts by weight of a triazin compound, and 1 to 30 parts by weight of an oxime compound.
[58] The photopolymerization initiator may further contain 0.01 to 10 parts by weight of a photo crosslinking accelerator that accelerates generation of a radical as an auxiliary component, or 0.01 to 10 parts by weight of a hardener that accelerates hardening.
[59] The photo crosslinking accelerator includes benzophenone compounds, such as benzophenone, 4,4-bis(dimethylamino)benzophenone,
4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylaminobenzophenone, methyl- o-benzoylbenzoate, 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone; fluorenone compounds, such as 9-fluorenone, 2-chloro-9-fluorenone, and 2-methyl-9-fluorenone; thioxanthone compounds, such as thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, l-chloro-4-propyloxy thioxanthone, isopropylthioxanthone, and diisopropylth- ioxanthone; xanthone compounds, such as xanthone and 2-methylxanthone; an an- thraquinone compounds, such as anthraquinone, 2-methyl anthraquinone, 2-ethyl an- thraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; acridine compounds, such as 9-phenylacridine, l,7-bis(9-acridinyl)heptane, l,5-bis(9-acridinylpentane), and l,3-bis(9-acridinyl)propane; dicarbonyl compounds, such as benzyl, l,7,7-trimethyl-bicyclo[2,2,l]heptane-2,3-dione, and 9,10-phenanthrenequinone; phosphine oxide compounds, such as 2,4,6-trimethybenzoyl diphenyl phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentene phosphine oxide; benzophenone compounds, such as methyl-4-(dimethylamino)-benzoate, ethyl- 4-(dimethylamino)-benzoate, and 2-n-butoxyethyl-4(dimethylamino)-benzoate; amino synergists, such as 2,5-bis(4-dimethylaminobenzal)cyclopentanone, 2,6-bis(4-diethylaminobenzal)cyclohexanon, and
2,6-bis(4-diethylaminobenzal)-4-methyl-cyclopentanone; coumarin compounds, such as 3,3-carbonylvinyl-7-(diethylamino)coumarin,
3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-benzoyl-7-(diethylamino)coumarin, 3-benzoyl-7-methoxy-coumarin, and 10, 10-carbornylbis[ 1 , 1 ,7,7-tetramethyl-2,3,6,7-tetrahydro- 1H,5H, 1 IH-Cl] -benzopyrano [6,7,8-ij]-quinolizin-ll-on; chalcone compounds, such as 4-diethylamino chalcone, and 4-azidebenzalacetophenone; and 2-benzoylmethylene, or 3-methyl-b-naphthothiazoline.
[60] Further, the hardener may be 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole,
2-mercaptobenzoxazole, 2,5-dimercapto- 1 ,3,4-thiadiazole, 2-mercapto-4,6-dimethylaminopyridine, pentaerythritol- tetrakis(3-mercaptopropionate), pentaerythritol-tris(3-mercaptopropionate), pen- taerythritol-tetrakis (2-mercaptoacetate) , pentaerythritol-tris (2-mercaptoacetate) , trimethylolpropane-tris(2-mercaptoacetate), or trimethylolpropane- tris (3 -mercaptopropionate) .
[61] In consideration of solubility, pigment dispersability, and coating, the solvent, used in the present invention, may be propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanon, 2-heptanon, 3-heptanon, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl- 3-ethoxypropionate, ethyl-3-ethoxypropionate, butylacetate, amylpermate, isoamylacetate, isobutylacetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate, or γ-butyrolacetate. The solvent may be independently used or the resultant obtained by mixing two or more kinds of solvents may be used as the solvent.
[62] The photoresist composition that is used in the present invention may additionally use 6) a primary additive that is at least one selected from the group consisting of a dispersing agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, a thermal polymerization preventing agent, and a leveling agent.
[63] The dispersing agent may be used by a method in which the dispersing agent is internally added to a pigment in a form of performing surface treatment on the pigment in advance, or a method in which the dispersing agent is externally added to the pigment. The dispersing agent may be a polymeric dispersing agent, a nonionic dispersing agent, an anionic dispersing agent or a cationic dispersing agent. Examples of the dispersing agent may include polyalkyleneglycol and ester thereof, poly- oxyalkylene polyhydric alcohol, esteralkylene oxide additive, alcohol alkylene oxide additive, sulfonate ester, sulphonate, carboxylic ester, carboxylate, alkylami- dalkyleneoxide additive, and alkylamine. These materials may be independently added or added after mixing two or more kinds of materials.
[64] The adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vin yl tris(2-methoxyethoxy)-silane, N- (2- aminoethyl) - 3 -aminopropylmethyldimethoxy silane, N-
(2-aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane,
3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
[65] As the antioxidant, 2,2-thiobis(4-methyl-6-t-butylphenol), or 2,6-g,t-butylphenol may be used, and as the ultraviolet absorber,
2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazol, or alkoxy ben- zophenone may be used.
[66] Further, the thermal polymerization preventing agent may be hydroquinone, p- methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis(3-methyl-6-t-butylphenol), 2,2-methylene bis(4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.
[67] The photoresist composition may further include 7) a secondary additive that is at least one selected from the group consisting of a carbon black dispersion, a resin binder having functionality, a monomer, a radiation-sensitive compound, and other additives.
[68] The present invention provides a black matrix for a liquid crystal display that is manufactured according to a manufacturing method comprising steps of 1) applying a black matrix photoresist composition for a liquid crystal display according to the present invention to a panel; and 2) exposing and developing the applied black matrix photoresist composition.
[69] The black matrix for the liquid crystal display is advantageous in that a developing property, a light shielding property, and an insulating property are excellent, a residue does not exist, and defective display can be prevented from occurring due to heat treatment.
[70] Further, the present invention provides a liquid crystal display that comprises the black matrix for the liquid crystal display. The liquid crystal display can be manufactured using a general manufacturing method that can be easily recognized by those skilled in the art, except that the liquid crystal display comprises the black matrix for the liquid crystal display according to the present invention. Mode for the Invention
[71] Hereinafter, for the purpose of better understanding for the present invention, the preferred embodiments of the present invention are disclosed. However, the embodiments are illustrative, and the present invention should not be construed as being limited to the embodiments set forth herein. [72] <EXAMPLE>
[73] EXAMPLE 1
[74] 750 parts by weight of a carbon black dispersion as a coloring agent (MIKUNI
CORPORATION, content of carbon black is 20%), 60 parts by weight of a compound[molar ratio
42(benzyl(meth)acrylate)/8(styrene)/6(N-phenylmaleimide)/20(glycidyl additive)/24(succinic anhydride), Mw = 12,000, acid value: 62 KOH mg/g, and double bond equivalent: 494] that is obtained by ring-opening reaction, using succinic anhydride, on a portion of an alcohol radical, which is generated by adding glycidyl- methacrylate to a benzyl(meth)acrylate/styrene/N-phenylmaleimide/(meth)acrylic acid copolymer as an alkali- soluble resin binder, 70 parts by weight of dipentaerythritolhex- aacrylate as a functional monomer, 10 parts by weight of ethanon,-l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,l-(o-acetyloxime) as a photopoly- merization initiator, 10 parts by weight of
2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, 5 parts by weight of mercaptobenzothiazole, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion promoter, 1 part by weight of a leveling agent, 510 parts by weight of propylene glycol monomethyl ether acetate and 510 parts by weight of 3-methoxybutyl acetate as a solvent, are mixed. Then, the obtained mixture is stirred for 5 hours, so as to prepare a black matrix photoresist composition.
[75] The photoresist composition solution prepared by the above-described method is spin-coated onto glass and prebaked at the temperature of about 1000C for 2 minutes, thereby forming a coating film having the thickness of approximately 1.29 μm. Then, the substrate is cooled down at the room temperature, and exposed with energy of 60 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 250C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O0C for 30 minutes in a convection oven.
[76] In the coating film pattern that is obtained by the above-described method, the thickness is 1.1 μm, the pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding property is obtained.
[77] <Sensitivity test>
[78] When measuring a change in thickness according to an exposure while using the photoresist composition obtained in EXAMPLE 1 and changing the exposure to 20, 30, 40, 50, 60, 70, 80, 90, or 100 mJ/cm2, a remaining rate of 90% or more is obtained at the exposure of 30 mJ/cm or more (see FIG. 1). [79] <Developing property (process margin) test>
[80] The photoresist composition obtained in EXAMPLE 1 is spin-coated onto glass and prebaked at the temperature of about 1000C for 2 minutes, thereby forming the coating film having the thickness of about 1.29 μm. Then, the substrate is cooled down at the room temperature, and exposed with the energy of 60 mJ/cm using the photomask under the high pressure mercury lamp. The exposed substrate is developed using the spray method in a KOH aqueous solution of 0.04% at the temperature of 250C. At this time, while the development time is controlled in a range of 60 to 90 seconds, the process margin is tested. According to the experimental result, a line width rarely changes through the development time in a ragnge of 50 to 90 seconds, and stability in pattern is maintained (see FIG. 2).
[81] EXAMPLE 2
[82] 750 parts by weight of a carbon black dispersion as a coloring agent (MIKUNI
CORPORATION, content of carbon black is 20%), 30 parts by weight of a compound[molar ratio
42(benzyl(meth)acrylate)/8(styrene)/6(N-phenylmaleimide)/34(glycidyl additive)/ 10(succinic anhydride), Mw = 10,000, acid value: 27 KOH mg/g, double bond equivalent 462] that is obtained by ring-opening reaction, using succinic anhydride, on a portion of an alcohol radical, which is generated by adding glycidyl- methacrylate to a benzyl(meth)acrylate/styrene/N-phenylmaleimide/(meth)acrylic acid copolymer as an alkali- soluble resin binder, 30 parts by weight of a benzyl(meth)acrylate/styrene/N-phenylmaleimide/(meth)acrylic acid/acrylic acid- glycidylmetacrylate polymer[molar ratio
52(benzyl(meth)acrylate)/8(styrene)/6(N-phenylmaleimide)/28(meth)acrylic acid/ 6(glycidyl additive), Mw = 18,000, acid value: 106 KOH mg/g, double bond equivalent: 2,466], 70 parts by weight of dipentaerythritolhexaacrylate as a functional monomer, 10 parts by weight of ethanon- l-(9-ethyl)-6-(2-methylbenzoyl-3-yl)-,l-(o-acetyloxime) as a photopolymerization initiator, 10 parts by weight of
2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, 5 parts by weight of mercaptobenzothiazole, 5 parts by weight of 3-methacryloxypropyltrimethoxysilane as an adhesion accelerator, 1 part by weight of a leveling agent, 510 parts by weight of propylene glycol monomethyl ether acetate and 510 parts by weight of 3-methoxybutyl acetateas a solvent, are mixed. Then, the obtained mixture is stirred for 5 hours, thereby manufacturing a black matrix photoresist composition.
[83] The photoresist composition prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the thickness is 1.1 μm, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
[84] EXAMPLE 3
[85] A photoresist composition having the same component ratio as that in EXAMPLE 1 is prepared, except that EXAMPLE 3 uses 60 parts by weight of a compound[molar ratio 50(benzyl(meth)acrylate)/8(styrene)/6(N-phenylmaleimide)/24(meth)acrylic acid)/12(glycidyl additive), Mw = 16,000, acid value: 87 KOH mg/g, double bond equivalent 1,289], which is generated by adding glycidylmethacrylate to a benzyl(meth)acrylate/styrene/N-phenylmaleimide/(meth)acrylic acid copolymer as an alkali- soluble resin binder.
[86] The photoresist composition that is prepared using the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the thickness is 1.1 μm, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
[87] EXAMPLE 4
[88] A black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 4 uses 10 parts by weight of l,2-octadione,-l-(4-phenylthio)phenyl,-2-(o-benzoyloxime), 10 parts by weight of 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, and 5 parts by weight of mercaptobenzothiazole, as photopolymerization initiators.
[89] The photoresist composition solution obtained in the above-described method is spin-coated onto alkali-free glass and prebaked at the temperature of about 1000C for 2 minutes, thereby forming a coating film having the thickness of about 1.3 μm. Then, the substrate is cooled down at the room temperature, and exposed with energy of 80 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 250C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O0C for 30 minutes in a convection oven.
[90] The photoresist composition solution that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the thickness is 1.1 μm, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
[91] EXAMPLE 5
[92] A black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 5 uses 30 parts by weight of 2-benzyl-2-(dimethylamino)-l-(4-morpholinophenyl)buthyl-l-on, 10 parts by weight of 2,2'-bis(o-chlorophenyl)-4,4,5,5'-tetraphenyl-l,2'-biimidazole, 10 parts by weight of 4,4-bis(diethylamino)benzophenone, and 5 parts by weight of mercaptobenzothiazole, as photopolymerization initiators.
[93] The photoresist composition solution obtained in the above-described method is spin-coated onto alkali-free glass and prebaked at the temperature of about 1000C for 2 minutes, thereby forming a coating film having the thickness of about 1.37 μm. Then, the substrate is cooled down at the room temperature, and exposed with energy of 80 mJ/cm using a photomask under a high pressure mercury lamp. After the exposed substrate is developed using a spray method in an aqueous KOH solution of 0.04% at the temperature of 250C, the substrate is washed with pure water, dried, and post-baked at the temperature of 22O0C for 30 minutes in a convection oven.
[94] The photoresist composition solution that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the thickness is 1.1 μm, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding characteristic is obtained.
[95] EXAMPLE 6
[96] A black matrix photoresist composition is prepared with the same composition as that in EXAMPLE 1, except that EXAMPLE 6 uses 60 parts by weight of a compound [molar ratio
35 (benzyl(meth)acrylate)/ 10(styrene)/ 10(dicyclopentanylmethacrylate)/20(glycidyl additive)/25 (succinic anhydride additive), Mw = 10,000, acid value: 63 KOH mg/g, double bond equivalent: 492] that is obtained by ring-opening reaction, using succinic anhydride, on a portion of an alcohol radical, generated by adding glycidyl- methacrylate to a benzyl(meth)acrylate/styrene/dicyclopentanylmethacrylate/(meth)acrylic acid copolymer as a binder.
[97] The photoresist composition prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the thickness is 1.1 μm, a pattern is not omitted, straightness is excellent, and a clear pattern characteristic is obtained without the contamination of an exposure portion. The optical density is 4.0 or more and an excellent light shielding characteristic is obtained. [98] COMPARATIVE EXAMPLE 1
[99] A black matrix photoresist composition having the same components as those in
EXAMPLE 1 is prepared, except that COMPARATIVE EXAMPLE 1 uses 60 parts by weight of a compound [molar ratio 35(benzyl(meth)acrylate)/25(glycidyl additive)/40(succinic anhydride additive), Mw = 12,000, acid value: 89 KOH mg/g, double bond equivalent: 386] that is obtained by ring-opening reaction, using succinic anhydride, on a portion of an alcohol radical, generated by adding glycidyl- methacrylate to a benzyl(meth)acrylate/(meth)acrylic acid copolymer as the alkali- soluble resin binder in EXAMPLE 1.
[100] The photoresist composition that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1. As a result, in the obtained coating film pattern, the pattern is omitted due to development, and an excellent pattern characteristic cannot be obtained.
[101] COMPARATIVE EXAMPLE 2
[102] A black matrix photoresist composition having the same components as those in
EXAMPLE 1 is prepared, except that COMPARATIVE EXAMPLE 2 uses 60 parts by weight of a compound[molar ratio 55(benzyl(meth)acrylate)/20((meth)acrylic acid)/25(glycidyl additive), Mw = 12,000, acid value: 65 KOH mg/g, double bond equivalent: 686] that is obtained by adding glycidylmethacrylate to a benzyl(meth)acrylate/(meth)acrylic acid copolymer as the alkali-soluble resin binder in EXAMPLE 1.
[103] The photoresist composition that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1, and is then developed. As a result, a development time is too lengthened and thus it is difficult to obtain a pattern. Further, straightness of a developed pattern and a film characteristic are bad.
[104] COMPARATIVE EXAMPLE 3
[105] A black matrix photoresist composition having the same components as those in
EXAMPLE 1 is prepared, except that COMPARATIVE EXAMPLE 3 uses 60 parts by weight of a compound[molar ratio 55(benzyl(meth)acrylate)/40((meth)acrylic acid)/5(glycidyl additive), Mw = 12,000, acid value: 157 H mg/g, double bond equivalent: 2858] that is obtained by adding glycidylmethacrylate to a benzyl(meth)acrylate/(meth)acrylic acid copolymer as the alkali-soluble resin binder in EXAMPLE 1.
[106] The photoresist composition that is prepared in the above-described method is subjected to various processes in the same method as that of EXAMPLE 1, and is then developed. As a result, a development is fast and thus a pattern is omitted.

Claims

Claims
[1] A black matrix photoresist composition for a liquid crystal display, comprising, on the basis of 100 parts by weight of the black matrix photoresist composition:
1) 1 to 40 parts by weight of a coloring agent containing a black pigment;
2) 1 to 20 parts by weight of an alkali- soluble resin binder represented by the following Formula 1 ;
3) 1 to 20 parts by weight of a multifunctional monomer having an ethylenically unsaturated double bond;
4) 0.1 to 20 parts by weight of a photopolymerization initiator; and
5) 30 to 90 parts by weight of a solvent; [Formula 1]
A B
Figure imgf000021_0001
(wherein, Rl indicates hydrogen, or a radical that forms an imide structure or a five-membered cyclic carboxylic anhydride together with X,
R2 is selected from the group consisting of hydrogen, methyl, and hydroxy methyl,
R3 and R4 are the same or different from each other, and are independent hydrogen or methyl,
X is selected from the group consisting of C to C alkyl esters, C to C alkyl esters substituted with 1 or 2 hydroxy groups, C 2 to C 6 alkyl esters substituted with C to C alkoxy groups, C to C alkyl esters substituted with halogen groups, C to C alkoxy poly(n = 2 to 30) alkylenes, C and C glycol esters, C to C alkyl esters substituted with phenyl groups, phenyl substituted with C to C
6 1 6 alkyl groups, phenyl substituted with C to C alkoxy groups, phenyl substituted
1 6 with a halogen group, C to C alkoxy methyl groups, glycidoxy methyl groups,
1 6 and a radical that forms an imide structure or a five-membered cyclic carboxylic anhydride together with Rl,
Y is selected from the group consisting of C to C alkylenes and C to C
0 12 3 60 alkylene esters that include 1 to 10 ester groups,
Z is selected from the group consisting of ethylene, propylene, butylene,
1 ,2-phenylene, 1 ,2-cyclohexylene,
Figure imgf000022_0001
(where * indicates a connection portion), and a, b, c, and d indicate molar ratios of A, B, C, and D, respectively, and a is in a range of 10 to 90, b is in a range of 0 to 60, c is in a range of 0 to 40, and d is in a range of 0 to 40).
[2] The black matrix photoresist composition according to claim 1, wherein the coloring agent containing a black pigment is a mixture of carbon black and at least one coloring pigment.
[3] The black matrix photoresist composition according to claim 2, wherein the carbon black is selected from SEAST 5HIISAF-HS, SEAST KH, SEAST 3HHAF-HS, SEAST NH, SEAST 3M, SEAST 300HAF-LS, SEAST 116HMMAF-HS, SEAST 116MAF, SEAST FMFEF-HS, SEAST SOFEF, SEAST VGPF, SEAST SVHSRF-HS, and SEAST SSRF (commercially available from Tokai Carbon Co., Ltd.); DIAGRAM BLACK II, DIAGRAM BLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, #CF9, #95, #3030, #3050, MA7, MA77, MA8, MAI l, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B (commercially available from Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX- 140U, PRINTEX- 140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (commercially available from Degussa Japan Company); and RAVEN- 1100ULTRA, RAVEN- 1080ULTRA, RAVEN- 1060ULTRA, RAVEN- 1040, RAVEN- 1035, RAVEN- 1020, RAVEN- 1000, RAVEN- 890H, RAVEN-890, RAVEN-88OULTRA, RAVEN- 860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN- 780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN- 2500ULTRA, RAVEN-2000, RAVEN- 1500, RAVEN- 1255, RAVEN- 1250, RAVEN- 1200, RAVEN- 1190ULTRA, and RAVEN- 1170 (commercially available from Columbia Carbon Co.).
[4] The black matrix photoresist composition according to claim 2, wherein a colorin g pigment that is mixed with the carbon black is selected from Carmine 6B (CI. 12490), Phthalocyanine Green (CI. 74260), Phthalocyanine Blue (CI. 74160), Mitsubishi Carbon Black MAlOO, Perylene Black (BASF K0084 and K0086), Cyanine Black, Lionol Yellow (CI. 21090), Lionol Yellow GRO (C.I.21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI. 42595), CI. PIGMENT RED 97, 122, 149, 168, 177, 180, 192, 215; CL Pigment Green 7, 36; CL PIGMENT 15:1, 15:4, 15:6, 22, 60, 64; CL PIGMENT 83, 139; and CL PIGMENT VIOLET 23.
[5] The black matrix photoresist composition according to claim 1, wherein at least one monomer used to form the A portion of the alkali- soluble resin binder represented by Formula 1 is selected from the group consisting of unsaturated carboxylic acid esters, such as benzyl (meth) aery late, methyl(meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, ethylhexyl(meth)acrylate, 2-phenoxyethyl( meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-chloropropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, acyloctyloxy-2-hydroxypropyl(meth)acrylate, glycerol(meth)acrylate, 2-methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, ethoxydiethylene glycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, methoxytripropy- leneglycol(meth)acrylate, poly(ethyleneglycol)methylether (meth)acrylate, phe- noxydiethyleneglycol(meth)acrylate, p- nonylphenoxypolyethyleneglycol(meth)acrylate, p-nonylphenoxypolypropylene glycol(meth)acrylate, glycidyl(meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1 ,3,3,3-hexafluoroisopropyl(meth)acrylate, octafluoropentyl(meth)acrylate, heptadecafluorodecyl(meth)acrylate, tribromophenyl(meth)acrylate, dicyclopen- tanylmethacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethy- lacrylate, isobornylmethacrylate, adamantylmethacrylate, methyl α- hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α- hydroxymethylacrylate, and butyl α-hydroxymethylacrylate; aromatic vinyls, such as styrene, α-methylstyrene, (o,m,p)-vinyltoluene, (o,m,p)-methoxystyrene, and (o,m,p)-chlorostyrene; unsaturated ethers, such as vinyl methy lether, vinyl ethyl ether, and allyl glycidyl ether; unsaturated imides, such as N- phenylmaleimide, N-(4-chlorophenyl)maleimide, N- (4-hydroxyphenyl)maleimide, and N- cyclohexylmaleimide; and maleic anhydrides, such as maleic anhydride and methyl maleic anhydride.
[6] The black matrix photoresist composition according to claim 1, wherein at least one monomer used to form the B portion of the alkali-soluble resin binder represented by Formula 1 is selected from the group consisting of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5-norbornene-2-carboxylic acid, mono-2-((meth)acryloyloxy)ethyl phthalate, mono-2-((meth)acryloyloxy)ethyl succinate, and ω-carboxy poly- caprolactone mono(meth)acrylate.
[7] The black matrix photoresist composition according to claim 1, wherein the alkali- soluble resin binder represented by Formula 1 is manufactured by a manufacturing method comprising steps of: i) preparing a polymer composed of A and B portions in Formula 1 by polymerizing a monomer used to form the A portion and a monomer used to form the B portion in Formula 1 ; ii) subjecting a partial acid radical of the B portion in the polymer prepared in the step of i) and an epoxy radical of glycidyl(meth)acrylate to a condensation reaction to prepare a polymer composed of A, B, and C in Formula 1; and iii) reacting a partial hydroxy group of the C portion of the polymer prepared in the step of ii) and carboxylic anhydride to form a D portion in Formula 1.
[8] The black matrix photoresist composition according to claim 7, wherein the carboxylic anhydride in the step of iii) is selected from succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, hexahydrophthalic anhydride, cis-l,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, itaconic anhydride, trimellic anhydride, and cis- 5-norbornene-endo-2,3-dicarboxylic anhydride.
[9] The black matrix photoresist composition according to claim 1, wherein, in the alkali- soluble resin binder represented by Formula 1, b is in a range of 5 to 60 when d is in a range of 0 to less than 5, and in a range of 0 to 10 when d is in a range of 5 to 40.
[10] The black matrix photoresist composition according to claim 1, wherein the alkali- soluble resin binder represented by Formula 1 satisfies the conditions 50 <P < 150, 1000 <Q <2500, and 1500 < (10xP)+Q < 4000 when d is in a range of O to less than 5, and the conditions 20 <P < 80, 400 <Q < 1000, and 500 ( (10xP)+Q ( 1500 when d is in a range of 5 to 40 (P indicates an acid value (KOH mg/g) and Q indicates a double bond equivalent).
[11] The black matrix photoresist composition according to claim 1, wherein the alkali- soluble resin binder represented by Formula 1 has a weight average molecular weight in a range of 1,000 to 200,000.
[12] The black matrix photoresist composition according to claim 1, wherein the multifunctional monomer having the ethylenically unsaturated double bond comprises a compound that has at least one unsaturated radical which is capable of being additionally polymerized with a boiling point of 1000C or more, or a functional monomer into which caprolactone in introduced.
[13] The black matrix photoresist composition according to claim 1, wherein the pho- topolymerization initiator comprises at least one compound that is selected from the group consisting of acetophenone compounds, biimidazole compounds, triazine compounds, and oxime compounds.
[14] The black matrix photoresist composition according to claim 1, wherein the pho- topolymerization initiator further comprises 0.01 to 10 parts by weight of a photo crosslinking accelerator or 0.01 to 10 parts by weight of a hardener.
[15] The black matrix photoresist composition according to claim 1, wherein the solvent comprises one or more of propyleneglycol monomethyl ether, ethyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, diethyleneglycol dimethyl ether, cyclohexanon, 2-heptanon, 3-heptanon, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl- 3-ethoxypropionate, ethyl-3-ethoxypropionate, butylacetate, amylpermate, isoamylacetate, isobutylacetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate, and γ-butyrolacetate.
[16] The black matrix photoresist composition according to claim 1, further comprising:
6) a primary additive that is at least one selected from the group consisting of a dispersing agent, an adhesion accelerator, an antioxidant, a ultraviolet absorber, a thermal polymerization preventing agent, and a leveling agent.
[17] The black matrix photoresist composition according to claim 1, further comprising:
7) a secondary additive that is at least one selected from the group consisting of a carbon black dispersion, a resin binder having functionality, a monomer, and a radiation-sensitive compound.
[18] A black matrix for a liquid crystal display that is manufactured by a manufacturing method comprising steps of:
I) applying the black matrix photoresist composition for the liquid crystal display of any one of claims 1 to 17 to a panel; and II) exposing and developing the applied black matrix photoresist composition. [19] A liquid crystal display comprising the black matrix for the liquid crystal display according to claim 18.
PCT/KR2007/006818 2006-12-26 2007-12-26 Black matrix high sensitive photoresist composition for liquid crystal display and black matrix prepared by using the same WO2008078953A1 (en)

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