CN107844029B - Use of colored photosensitive resin composition in color filter - Google Patents

Use of colored photosensitive resin composition in color filter Download PDF

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CN107844029B
CN107844029B CN201710796753.1A CN201710796753A CN107844029B CN 107844029 B CN107844029 B CN 107844029B CN 201710796753 A CN201710796753 A CN 201710796753A CN 107844029 B CN107844029 B CN 107844029B
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chemical formula
resin composition
photosensitive resin
colored photosensitive
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CN107844029A (en
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金荣圣
吴相旼
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • 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
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
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  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provides a colored photosensitive resin composition, a color filter and an image display device, wherein the colored photosensitive resin composition is characterized by comprising an alkali-soluble resin containing a repeating unit represented by chemical formula 1 and a photopolymerization initiator containing at least one compound selected from the group consisting of compounds represented by chemical formula 2. In the chemical formula 1, R1And R2Each independently being a hydrogen atom or a methyl group, R3Is a residue containing a carboxylic acid derived from an acid anhydride, wherein R in the formula 24～R13Each independently of the others is hydrogen, halogen, C1～C20Alkyl of (C)6～C20Aryl of (C)1～C20Alkoxy group of (C)7～C40Arylalkyl of C1～C20Hydroxyalkyl of (C)2～C40Hydroxyalkoxyalkyl or C3～C20A cycloalkyl group of (a).
Figure DDA0001400519430000011

Description

Use of colored photosensitive resin composition in color filter
Technical Field
The present invention relates to a colored photosensitive resin composition, a color filter and an image display device manufactured by using the same.
Background
In general, in order to realize color image display, a color filter having a plurality of colored layers arranged so as to correspond to a plurality of pixels of an image display element is used in an image display device.
Such a color filter is not formed on the substrate (hereinafter, referred to as a TFT substrate) side on which a Thin Film Transistor (hereinafter, referred to as a TFT) having a switching element is formed, but is formed on the counter substrate side disposed to face the TFT substrate.
However, when the color filter is disposed on the counter substrate side, the positional arrangement with each pixel electrode on the TFT substrate is not simple, and the aperture ratio is reduced. Further, since the distance between the color filter and the liquid crystal layer is large, there occurs a problem that the display quality is degraded by light incident from an oblique direction. To solve such a problem, japanese patent laid-open No. h 09-73078 uses a COA (Color Filter on Array) method in which a Color Filter is formed on a TFT substrate.
In forming a color filter on the TFT substrate, a Contact hole (conductive path) is required to be formed in the process, and thus, it is actually necessary to develop a technique for adjusting the Contact hole.
In addition, in the case of forming a color filter on the TFT substrate, display defects due to instability of a pixel coating film may occur in an etching process and a reagent treatment, and thus, it is actually necessary to develop a technique for improving the display defects.
Korean registered patent No. 1,541,542 relates to a colored photosensitive resin composition characterized by containing a binder resin having a specific weight average molecular weight in order to adjust the difference in height (Ra) of the Overlap (Overlap) of colored layers formed of the colored photosensitive resin composition.
However, in the above document, although the problem with the development residue is solved, in addition to this, a solution to the display defect cannot be provided, and the problem with the contact hole that should be adjusted when forming the color filter on the above TFT substrate is not recognized at all.
Therefore, development of a colored photosensitive resin composition capable of improving various screen display defects and adjusting the size and shape of the contact hole is required.
Documents of the prior art
Patent document
Korean registered patent No. 1,541,542 (2015.07.28)
Disclosure of Invention
Problems to be solved
The purpose of the present invention is to provide a colored photosensitive resin composition which is capable of forming a contact hole with excellent alignment accuracy in an R, G, B resin film while improving the display defect of a screen that may occur when manufacturing a color filter of the COA system.
The present invention also provides a color filter and an image display device manufactured using the colored photosensitive resin composition.
Means for solving the problems
The colored photosensitive resin composition of the present invention for achieving the above object is characterized by comprising an alkali-soluble resin containing a repeating unit represented by the following chemical formula 1 and a photopolymerization initiator containing one or more compounds selected from the group consisting of compounds represented by the following chemical formula 2:
[ chemical formula 1]
Figure BDA0001400519410000021
(in the above-mentioned chemical formula 1,
R1and R2Each independently a hydrogen atom or a methyl group,
R3containing residues of carboxylic acids derived from anhydrides)
[ chemical formula 2]
Figure BDA0001400519410000031
(in the above-mentioned chemical formula 2,
R4～R13each independently of the others is hydrogen, halogen, C1～C20Alkyl of (C)6～C20Aryl of (C)1～C20Alkoxy group of (C)7～C40Arylalkyl of C1～C20Hydroxyalkyl of (C)2～C40Hydroxyalkoxyalkyl or C3～C20Cycloalkyl group of (ii).
The present invention also provides a color filter comprising a cured product of the colored photosensitive resin composition, and an image display device comprising the color filter.
Effects of the invention
The colored photosensitive resin composition of the present invention for achieving the above object has advantages that a contact hole having excellent alignment accuracy can be formed in R, G, B resin film by including an alkali-soluble resin containing a repeating unit having a specific structure and a photopolymerization initiator represented by a specific chemical formula, thereby improving display defects of a screen which may occur when manufacturing a color filter of the COA system.
In addition, the color filter manufactured by the colored photosensitive resin composition and the image display device comprising the color filter have the effect of improving poor display of a picture.
Drawings
FIG. 1 is a process diagram for forming a color filter by the COA method using the colored photosensitive resin composition of the present invention.
Description of the symbols
1: TFT substrate
2: pixel pattern
3: TFT element
4: nitride film (SiNx)
Detailed Description
The present invention will be described in more detail below.
In the present invention, when it is stated that a certain member is located "on" another structure, it includes not only a case where the certain member is in contact with another structure but also a case where another member exists between the two members.
In the present invention, when a part is referred to as "including" a certain component, it means that other components may be further included without excluding other components unless otherwise stated.
< colored photosensitive resin composition >
One embodiment of the present invention relates to a colored photosensitive resin composition, which comprises an alkali-soluble resin containing a repeating unit represented by the following chemical formula 1 and a photopolymerization initiator containing one or more compounds selected from the group consisting of compounds represented by the following chemical formula 2.
[ chemical formula 1]
Figure BDA0001400519410000041
(in the above-mentioned chemical formula 1,
R1and R2Each independently a hydrogen atom or a methyl group,
R3containing residues of carboxylic acids derived from anhydrides)
[ chemical formula 2]
Figure BDA0001400519410000042
(in the above-mentioned chemical formula 2,
R4～R13each independently of the others is hydrogen, halogen, C1～C20Alkyl of (C)6～C20Aryl of (C)1～C20Alkoxy group of (C)7～C40Arylalkyl of C1～C20Hydroxyalkyl of (C)2～C40Hydroxyalkoxyalkyl or C3～C20Cycloalkyl group of (ii).
Alkali soluble resin
The alkali-soluble resin of the present invention is characterized by containing a repeating unit represented by the following chemical formula 1.
The alkali-soluble resin generally has reactivity and alkali solubility due to the action of light or heat, and can function as a dispersion medium for solid components represented by a colorant and also function as a binder resin.
[ chemical formula 1]
Figure BDA0001400519410000051
(in the above-mentioned chemical formula 1,
R1and R2Each independently a hydrogen atom or a methyl group,
R3is a residue containing a carboxylic acid derived from an anhydride. )
The alkali-soluble resin of the present invention, which contains the repeating unit of the above chemical formula 1, has the following advantages: when a color pattern is formed from the colored photosensitive resin composition containing the alkali-soluble resin, the difference in height of the pattern caused by the colorant contained in the colored photosensitive resin composition can be minimized, thereby remarkably improving smoothness and manufacturing a color filter having excellent transmittance.
In addition, in the case where the glass transition temperature (Tg) of the alkali-soluble resin containing the repeating unit represented by the above chemical formula 1 may be less than 0 ℃, the development speed of the colored photosensitive resin composition including the alkali-soluble resin may be significantly increased and the adhesion force may be improved, thereby having an effect of being able to suppress the problem of the step of the pattern caused by the increase of the development speed.
The content of the repeating unit represented by the above chemical formula 1 may be 50 to 90 mol%, specifically 55 to 85 mol%, more specifically 60 to 75 mol% with respect to the entire mol% of the alkali-soluble resin.
When the content of the repeating unit represented by the above chemical formula 1 is within the above range, there is an advantage in that the glass transition temperature of the alkali-soluble resin including the repeating unit is easily made lower than 0 ℃.
According to an embodiment of the present invention, the alkali-soluble resin of the present invention may be produced by copolymerizing a monomer (a1) containing the repeating unit represented by the above chemical formula 1 and a copolymerizable monomer (a2) having an unsaturated double bond.
The kind of the copolymerizable unsaturated double bond-containing monomer (a2) is not particularly limited. Specific examples thereof include aromatic vinyl compounds such as styrene, vinyltoluene, α -methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; n-substituted maleimide compounds such as N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [ 5.2.1.02, 6] decan-8-yl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; hydroxyethyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; unsaturated oxetane compounds such as 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like. The above monomers may be used each alone or in combination of two or more.
The content of the copolymerizable unsaturated double bond-containing monomer (a2) is not particularly limited, and for example, may be 10 to 50 mol%, preferably 25 to 40 mol%, based on the total mol% of the monomers used for polymerizing the alkali-soluble resin. In the case of satisfying the above range, there is an advantage in that the glass transition temperature of the resin shows less than 0 ℃ to be able to minimize the step difference.
A method for producing an alkali-soluble resin according to another embodiment of the present invention is as follows.
Conventionally, an alkali-soluble resin of a colored photosensitive resin composition is produced by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to be soluble in an alkali developing solution used in a developing treatment step in forming a pattern. However, the alkali-soluble resin formed by such a production method has a problem that it is difficult to produce a resin having a glass transition temperature of less than 0 ℃ because the main chain contains a carboxyl group.
However, the alkali-soluble resin of the present invention can be produced in such a manner that a carboxyl group exists in a side chain rather than in a main chain participating in a polymerization reaction, and thus an alkali-soluble resin having a glass transition temperature of less than 0 ℃ can be produced while imparting suitable developability.
On the other hand, in one embodiment of the method for producing an alkali-soluble resin, the method may include: (S1) a step of polymerizing glycidyl (meth) acrylate (a1) with monomer (a2) having an unsaturated double bond; (S2) a step of reacting the copolymer produced above with an ethylenically unsaturated monomer having a carboxyl group; and (S3) a step of reacting the copolymer reacted as described above with an acid anhydride.
The step (S2) is a step of imparting photocurability to the alkali-soluble resin of the present invention, and the type of the ethylenically unsaturated monomer having a carboxyl group in the step (S2) is not particularly limited as long as it functions, and examples thereof include (meth) acrylic acid, ethyl acrylate, and/or butyl acrylate, and specifically methacrylic acid.
The step (S3) is a step of giving an appropriate acid value to the alkali-soluble resin of the present invention, and more specifically, a step of introducing a carboxyl group into a side chain of the alkali-soluble resin by reacting a hydroxyl group derived from a glycidyl group of the alkali-soluble resin with an acid anhydride.
The type of acid anhydride used in the step (S3) is not particularly limited as long as it functions, and examples thereof include Phthalic anhydride (Phthalic anhydride), (2-Dodecen-1-yl) Succinic anhydride ((2-Dodecen-1-yl) Succinic anhydride), Maleic anhydride (Maleic anhydride), Succinic anhydride (Succinic anhydride), Citraconic anhydride (Citraconic anhydride), Glutaric anhydride (Glutaric anhydride), Methylsuccinic anhydride (Methylsuccinic anhydride), 3-Dimethylglutaric anhydride (3,3-Dimethylglutaric anhydride), Phenylsuccinic anhydride (Phthalic anhydride), Itaconic anhydride (Itonic anhydride), 3,4,5,6-Tetrahydrophthalic anhydride (3,4,5,6-Tetrahydrophthalic anhydride), Hexahydrophthalic anhydride (Trimellitic anhydride), and the like, specifically, Maleic anhydride (Maleic anhydride), Phthalic anhydride (Phthalic anhydride), Trimellitic anhydride (trimelitic anhydride), Succinic anhydride (Succinic anhydride), Hexahydrophthalic anhydride (Hexahydrophthalic anhydride), and norbornene anhydride (carbonic anhydride) may be used, and more specifically, Trimellitic anhydride (trimelitic anhydride), Succinic anhydride (Succinic anhydride), and Hexahydrophthalic anhydride (Hexahydrophthalic anhydride) may be used from the viewpoint of price and easiness of reaction.
The acid value of the alkali-soluble resin of the present invention produced according to the above production method may be 30 to 150mgKOH/g in order to ensure compatibility with the dye contained in the composition and storage stability of the composition. When the acid value of the alkali-soluble resin is less than 30mgKOH/g, it may be difficult to secure a sufficient development speed in the colored photosensitive resin composition, and when it exceeds 150mgKOH/g, adhesion to a substrate is reduced, a short circuit of a pattern is likely to occur, and compatibility with a dye is likely to be a problem, and there may be a problem that a dye in the colored photosensitive resin composition precipitates or storage stability of the colored photosensitive resin composition is reduced, and viscosity is increased.
The content of the alkali-soluble resin containing the repeating unit represented by the above chemical formula 1 may be, for example, 1 to 80% by weight, specifically 5 to 75% by weight, more specifically 10 to 70% by weight, based on the total weight of solid components in the colored photosensitive resin composition. When the alkali-soluble resin content is within the above range, the solubility in the developer is sufficient, the pattern formation is easy, and the effect of preventing the decrease in the film of the pixel portion of the exposed portion and improving the exfoliation of the non-pixel portion can be expected.
Photopolymerization initiator
The photopolymerization initiator of the present invention is characterized by being one or more selected from the group consisting of compounds represented by the following chemical formula 2.
[ chemical formula 2]
Figure BDA0001400519410000081
(in the above-mentioned chemical formula 2,
R4～R13each independently of the others is hydrogen, halogen, C1～C20Alkyl of (C)6～C20Aryl of (C)1～C20Alkoxy group of (C)7～C40Arylalkyl of C1～C20Hydroxyalkyl of (C)2～C40Hydroxyalkoxyalkyl or C3～C20Cycloalkyl group of (ii).
Specifically, R is as defined above4～R13Each independently can be hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexyl, hydroxyisohexyl, hydroxymethylgroup, hydroxymethoxyethyl, hydroxymethylpropyl, hydroxymethoxybutyl, hydroxyethoxybutyl, hydroxyethoxyhexyl, hydroxymethoxypropyl, hydroxyethoxybutyl, or mixtures thereofAn oxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a hydroxyethoxyhexyl group, more specifically, the above-mentioned R4Can be hydrogen, methyl, ethyl, propyl or butyl; r5May be methyl, ethyl or propyl; r6Can be methyl, ethyl, propyl or butyl; r7～R13May be hydrogen.
The photopolymerization initiator of the present invention is selected from the group consisting of the compounds represented by the above chemical formula 2, thereby having the effect of improving sensitivity and curing degree.
Further, the photopolymerization initiator of the present invention has the following advantages by being used together with the alkali-soluble resin of the present invention: in the image display device having the COA structure, contact holes having excellent alignment accuracy can be formed in R, G, B resin films, and when electrical paths between pixel electrodes, which are the resin films, and active elements (TFTs) are formed, pattern stability of R, G, B resin films can be ensured during contact hole formation by dry etching and Indium Zinc Oxide (IZO) vapor deposition for use as pixel electrodes, and pixel defects caused by R, G, B disconnection for ensuring a high aperture ratio can be improved.
The alkyl group is a straight-chain or branched hydrocarbon radical consisting of only carbon and hydrogen atoms, having no unsaturation, and bonded to the rest of the molecule by a single bond. Specifically, the alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms, more specifically a linear or branched alkyl group having 1 to 10 carbon atoms, and still more specifically a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of such an unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a hexyl group. One or more hydrogen atoms contained in the above alkyl group may be replaced by a halogen atom, a hydroxyl group, a thiol group (-SH), a nitro group, a cyano group, a substituted or unsubstituted amino group, an amidino group, a hydrazine group or a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, or C1～C20Alkyl of (C)1～C20Halogenoalkyl of, C2～C20Alkenyl of, C2～C20Alkynyl of (A), C1～C20Heteroalkyl of (a), C6～C20Aryl of (C)6～C20Arylalkyl of C6～C20Heteroaryl of (A), or C6～C20Substituted with heteroarylalkyl.
The above-mentioned aryl groups are aromatic monocyclic or polycyclic hydrocarbon ring systems composed only of hydrogen and carbon, in which case the ring system may be partially or fully saturated. At least one or more hydrogen atoms in the aryl group may be substituted with the same substituent as in the case of the alkyl group. The aryl group is an organic radical derived from an aromatic hydrocarbon by removing one hydrogen, and may include a monocyclic or condensed ring system having 4 to 7, specifically 5 or 6 ring atoms in each ring, and may further include a form in which a plurality of aryl groups are connected by a single bond. The aryl group may contain 6 to 20 carbon atoms, and specifically may contain 6 to 18 carbon atoms.
The alkoxy group may be an oxygen-containing straight-chain or branched alkoxy group having an alkyl moiety of 1 to 20 carbon atoms. Specifically, the alkoxy group may have 1 to 10 carbon atoms, and more specifically, the alkoxy group may have 1 to 4 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a tert-butoxy group. The alkoxy group may be further substituted with one or more halogen atoms such as fluorine, chlorine, or bromine to provide a haloalkoxy group. Examples of such a compound include fluoromethoxy, chloromethoxy, trifluoromethoxy, trifluoroethoxy, fluoroethoxy, fluoropropoxy, and the like. One or more hydrogen atoms in the alkoxy group may be substituted by the same substituent as in the case of the alkyl group.
The arylalkyl group means that one or more hydrogen atoms of the alkyl group are substituted with the aryl group. The arylalkyl group may have 7 to 40 carbon atoms, specifically 7 to 28 carbon atoms, and more specifically 7 to 24 carbon atoms.
The hydroxyalkyl group means an OH-alkyl group in which a hydroxyl group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group means a hydroxyalkyl-O-alkyl group in which the hydroxyalkyl group and the alkyl group are bonded to each other through oxygen. The hydroxyalkyl group may have 1 to 20 carbon atoms, specifically 1 to 10 carbon atoms, and more specifically 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group may have 2 to 40 carbon atoms, specifically 2 to 20 carbon atoms, and more specifically 2 to 9 carbon atoms.
The cycloalkyl group includes not only monocyclic and polycyclic hydrocarbons, and at least one or more hydrogen atoms in the cycloalkyl group may be substituted with the same substituent as in the case of the alkyl group. The cycloalkyl group may have 3 to 20 carbon atoms, specifically 3 to 10 carbon atoms, and more specifically 3 to 8 carbon atoms.
The content of the photopolymerization initiator may be 0.1 to 40% by weight, specifically 0.5 to 35% by weight, more specifically 1 to 30% by weight, based on the total weight of solid components in the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, the following advantages are obtained: the colored photosensitive resin composition containing the photopolymerization initiator has high sensitivity, short exposure time, high productivity, high resolution, high pixel strength and high pixel surface smoothness.
The colored photosensitive resin composition according to an embodiment of the present invention may further contain, in addition to the photopolymerization initiator, a general photopolymerization initiator capable of polymerizing the photopolymerizable compound that the present invention may further contain, and may further contain a photopolymerization initiation aid as needed.
In this case, the content of the photopolymerization initiation aid may be 0.1 to 40% by weight, specifically 0.5 to 35% by weight, more specifically 1 to 30% by weight, based on the total solid content of the colored photosensitive resin composition, relative to the contents of the alkali-soluble resin and the photopolymerizable compound. When the content of the photopolymerization initiation aid is within the above range, there are advantages in that the sensitivity of the colored photosensitive resin composition containing the photopolymerization initiation aid is improved, and the productivity of a color filter produced by using the colored photosensitive resin composition is improved.
The colored photosensitive resin composition according to another embodiment of the present invention may further include one or more selected from the group consisting of a photopolymerizable compound, a colorant, a solvent, and an additive.
Photopolymerizable compound
The colored photosensitive resin composition according to an embodiment of the present invention may further contain a photopolymerizable compound.
The photopolymerizable compound is a compound polymerizable by the action of the photopolymerization initiator, and examples thereof include monofunctional monomers, difunctional monomers, and polyfunctional monomers.
The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone.
The type of the bifunctional monomer is not particularly limited, and examples thereof include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.
The polyfunctional monomer is not particularly limited in kind, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like.
The photopolymerizable compound may be contained in an amount of 5 to 45 wt%, specifically 6 to 44 wt%, more specifically 7 to 43 wt%, based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the intensity and smoothness of the pixel portion including the photopolymerizable compound can be improved.
Coloring agent
The colored photosensitive resin composition according to an embodiment of the present invention may further contain a colorant containing one or more pigments or one or more dyes.
Pigment (I)
The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be any of various pigments used in printing inks, inkjet inks, and the like, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, and bisperylene pigments
Figure BDA0001400519410000121
Oxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthrapyrimidine pigments, anthraxanthone (anthanthrone) pigments, indanthrone (indanthrone) pigments, flavanthrone pigments, pyranthrone (pyranthrone) pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complexes, and specific examples thereof include metal oxides and composite metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. In particular, as The organic pigment and The inorganic pigment, specifically, compounds classified as pigments in color index (published by The society of Dyers and Colourists), more specifically, pigments numbered by The following color index (c.i.) are mentioned, but not limited thereto, and they may be used alone or in combination of two or more kinds.
C.i. pigment yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185;
c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;
c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
c.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76;
c.i. pigment green 7, 10, 15, 25, 36, 47, 59, 62 and 63;
c.i pigment brown 28;
c.i pigment black 1 and 7; etc. of
The pigment may be an organic pigment or an inorganic pigment generally used in the art, and they may be used each alone or in combination of two or more.
Among the above-mentioned exemplary c.i. pigments, specifically, pigments selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150, c.i. pigment yellow 185, c.i. pigment orange 38, c.i. pigment red 122, c.i. pigment red 166, c.i. pigment red 177, c.i. pigment red 208, c.i. pigment red 242, c.i. pigment red 254, c.i. pigment red 255, c.i. pigment violet 23, c.i. pigment blue 15:3, pigment blue 15:6, c.i. pigment green 7, c.i. pigment green 36, and c.i. pigment green 58 can be used.
The pigment is preferably a pigment dispersion liquid in which the particle diameter is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing by adding a pigment dispersant, and a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained by the above method.
Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, zwitterionic, polyester and polyamine surfactants, and these may be used alone or in combination of two or more.
Pigment dispersants
The pigment dispersant is added for the purpose of disaggregation and maintenance of stability of the pigment, and any pigment dispersant generally used in the art can be used without limitation. Specifically, an acrylate-based dispersant (hereinafter, referred to as an acrylic dispersant) containing Butyl Methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) may be contained. In this case, the acrylic dispersant is preferably manufactured by the activity control method provided in Korean laid-open patent No. 2004-0014311, and examples of commercially available acrylic dispersants manufactured by the activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.
The above-exemplified acrylic dispersants may be used each alone or in combination of two or more.
The pigment dispersant may be a resin type pigment dispersant other than the acrylic dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, and particularly include oily dispersants such as polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and modified products thereof, or amides or salts thereof formed by reaction of polyesters having free (free) carboxyl groups with poly (lower alkylene imine); water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinyl pyrrolidone; a polyester; a modified polyacrylate; ethylene oxide/propylene oxide adducts; and phosphoric acid esters and the like. As a commercial product of the above resin type pigment dispersant, for example, a trade name of BYK chemical company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; trade name of BASF (BASF) corporation: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol (lubol) corporation: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; trade name of Chuanjian refining company: HINACT T-6000, HINACT T-7000, HINACT T-8000; trade name of ajinomoto corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; trade name of Kyoeisha chemical Co: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. The resin type pigment dispersants other than the above-mentioned acrylic dispersant may be used alone or in combination of two or more kinds, or may be used in combination with the acrylic dispersant.
The content of the pigment dispersant may be 5 to 60 parts by weight, specifically 10 to 55 parts by weight, more specifically 15 to 50 parts by weight, based on the total weight of solid components of the pigment used. When the content of the pigment dispersant exceeds the above range, the viscosity may be high, and when the content is less than the above range, problems such as difficulty in micronization of the pigment and gelation after dispersion may occur.
Dye material
The dye may be used without limitation as long as it has solubility in an organic solvent. Specifically, a dye having solubility in an organic solvent and also having solubility in an alkali developing solution, heat resistance, solvent resistance, and other reliability can be used.
As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye with a nitrogen-containing compound, a sulfonamide of an acid dye, or the like, and a derivative thereof may be used, and in addition thereto, an azo-based, xanthene-based, phthalocyanine-based acid dye, and a derivative thereof may be selected.
The dyes may be compounds classified into dyes in color index (published by the society of dyers) or known dyes described in the handbook of dyeing (color dyeing).
Specific examples of the above dye include c.i. solvent dyes:
c.i. yellow dyes such as solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163, etc.;
red dyes such as c.i. solvent red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179 and the like;
orange dyes such as c.i. solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62, etc.;
c.i. blue dyes such as solvent blue 5, 35, 36, 37, 44, 59, 67, 70, etc.;
c.i. violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49, etc.;
c.i. solvent green 1, 3,4,5, 7, 28, 29, 32, 33, 34, 35 and the like.
Among the c.i. solvent dyes, specifically, c.i. solvent yellow 14, 16, 21, 56, 151, 79, 93; c.i. solvent red 8, 49, 89, 111, 122, 132, 146, 179; c.i. solvent orange 41, 45, 62; c.i. solvent blue 35, 36, 44, 45, 70; c.i. solvent violet 13, more specifically, c.i. solvent yellow 21, 79; c.i. solvent red 8, 122, 132.
Further, as the c.i. acid dye, there may be mentioned:
c.i. yellow dyes such as acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, etc. red dye;
orange dyes such as c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, etc.;
c.i. acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1, 335, 340 and the like blue dye;
violet dyes such as c.i. acid violet 6B, 7, 9, 17, 19, 66;
c.i. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, and the like.
Among the acid dyes, specifically, c.i. acid yellow 42 having excellent solubility in organic solvents; c.i. acid red 92; c.i. acid blue 80, 90; c.i. acid violet 66; c.i. acid green 27.
Further, as the c.i. direct dye, there can be mentioned:
c.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141 and the like;
c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and the like red dye;
c.i. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. orange dyes;
c.i. direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, and the like blue dye;
c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like violet dye;
c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc.
Further, as the c.i. mediator dye, there may be mentioned:
yellow dyes such as c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like;
c.i. medium red 1, 2, 3,4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like red dye;
c.i. intermediate orange 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes;
c.i. medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like blue dye;
c.i. intermediate violet 1, 2, 4,5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like violet dye;
c.i. medium green 1, 3,4,5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like.
The above dyes may be used each alone or in combination of two or more.
The content of the colorant may be 5 to 60 parts by weight, specifically 7 to 50 parts by weight, more specifically 10 to 45 parts by weight based on the total weight of the solid components in the colored photosensitive resin composition. When the content of the colorant is within the above range, there is an advantage that even when a thin film is formed using the colored photosensitive resin composition, the color density of the pixel is sufficient, and the releasability of the non-pixel portion at the time of development is not lowered and generation of residue can be suppressed.
Solvent(s)
The colored photosensitive resin composition according to an embodiment of the present invention may further include a solvent.
The solvent is not particularly limited as long as it is effective in dissolving other components contained in the colored photosensitive resin composition, and a solvent used in a general colored photosensitive resin composition can be used, and specific examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters, and amides.
Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate, and butyl lactate; cyclic esters such as γ -butyrolactone.
In view of coating properties and drying properties, the solvent may be an organic solvent having a boiling point of 100 to 200 ℃, more specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, or the like.
The above-exemplified solvents may be used singly or in combination, and the content may be 60 to 90% by weight, specifically 65 to 88% by weight, more specifically 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is contained in the above range, the coating apparatus such as a roll coater, a spin coater, a slit coater (also referred to as a die coater), or an ink jet printer can be used to perform coating, and thus an excellent effect of coating property can be expected. If the content of the solvent is less than the above range, the coating property may be deteriorated, making the process difficult, and if the content exceeds the above range, the performance of the color filter formed of the red photosensitive resin composition may be deteriorated.
Additive agent
The colored photosensitive resin composition according to an embodiment of the present invention may further contain an additive as necessary.
Specifically, at least one selected from a dispersant, a wetting agent, a silane coupling agent, an anti-gelling agent, and the like can be used as the additive.
As the dispersant, a commercially available surfactant can be used, and examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and a mixture thereof. Examples of the silicone surfactant include surfactants having siloxane bonds. Examples of commercially available products include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone 29SHPA, Toray Silicone SH30PA, polyether-modified Silicone SH8400 (manufactured by Toray Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by TSGE TSToshiba Silicone Co., Ltd.). Examples of the fluorine-based surfactant include surfactants having fluorocarbon chains. Specifically, Fluorinert (trade name) FC430, Fluorinert FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (manufactured by Dainippon ink chemical Co., Ltd.), F-Top (trade name) EF301, F-Top EF303, F-Top EF351, F-Top EF352 (manufactured by New autumn chemical Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Nissuxu glass Co., Ltd.), E5844 (manufactured by Dajinghi Kagaku Co., Ltd.), BM-1000, BM-1100 (trade name: Chemie) and the like can be given as examples. Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (trade name) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by Dainippon ink chemical Co., Ltd.) are exemplified.
Examples of the humectant include glycerin, diethylene glycol, and ethylene glycol, and one or more selected from these may be contained.
Examples of the silane coupling agent include aminopropyltriethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, and the like, and commercially available products include SH6062, SZ6030 (manufactured by Toray-Dow Corning Silicone co., Ltd.), KBE903, KBM803 (manufactured by Shin-Etsu Silicone co., Ltd.), and the like.
The anti-gelling agent may be, for example, sodium polyacrylate. .
< color Filter >
Another embodiment of the present invention provides a color filter produced using the colored photosensitive resin composition.
The color filter includes a substrate and a pattern layer formed on the substrate.
The substrate is not particularly limited, and the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyether sulfone (PES), Polycarbonate (PC), or the like.
The pattern layer may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermally curing the applied layer in a predetermined pattern, as a layer containing the colored photosensitive resin composition of the present invention. The above-described pattern layer may be formed by performing a method generally known in the art.
The color filter including the substrate and the pattern layer may further include a partition wall formed between the patterns, or may further include a black matrix, but is not limited thereto.
In addition, the color filter may further include a protective film formed on the upper portion of the pattern layer of the color filter.
< image display apparatus >
Another embodiment of the present invention relates to an image display device including the color filter. In this case, the image display device may be a COA structure image display device in which a color filter is formed on a substrate on which a Thin Film Transistor (TFT) is formed. In the case where the colored photosensitive resin composition of the present invention is contained, the following advantages are obtained: in the image display device having the COA structure, when R, G, B a resin film is used to form a contact hole having excellent alignment accuracy and an electrical path is formed between a pixel electrode, which is the resin film, and an active element (TFT), pattern stability of R, G, B a resin film is ensured during formation of a contact hole by dry etching and IZO vapor deposition used as a pixel electrode, and pixel defects caused by R, G, B disconnection for ensuring a high aperture ratio are improved.
The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.
Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments of the present specification may be modified into various other forms, and the scope of the present specification should not be construed as being limited to the embodiments described in detail below. The embodiments of the present description are provided to more fully describe the present description to those skilled in the art. In addition, "%" and "part(s)" representing the contents are based on weight unless otherwise mentioned.
Synthesis example: alkali soluble resin (A-1)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. Into the flask were charged 100g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), 100g of Propylene Glycol Monomethyl Ether (PGME), 8.2g of Azobisisobutyronitrile (AIBN), 73.6g of 2-ethylhexyl acrylate, 5.9g of 4-methylstyrene, 78.1g of glycidyl methacrylate, and 6.1g of n-dodecylmercaptan, and the nitrogen gas was replaced. Thereafter, the temperature of the reaction solution was raised to 80 ℃ with stirring, and the reaction was carried out for 4 hours. After the temperature of the reaction solution was lowered to normal temperature and the atmosphere in the flask was replaced with nitrogen gas to air, 0.2g of triethylamine, 0.1g of 4-methoxyphenol and 39.6g of acrylic acid were charged, and the reaction was carried out at 100 ℃ for 6 hours. Thereafter, the temperature of the reaction solution was lowered to normal temperature, 6.0g of succinic anhydride was charged, and the reaction was carried out at 80 ℃ for 6 hours to synthesize an alkali-soluble resin (A-1).
The acid value of the alkali-soluble resin synthesized above was 32.8 mgKOH/g.
The weight average molecular weight (Mw) of the alkali-soluble resin synthesized above was 6,230 as measured by GPC, and the glass transition temperature was-21.0 ℃ as measured by a differential scanning calorimeter.
Preparation example: production of pigment Dispersion composition (D)
30 parts by weight of c.i. pigment blue 15:6 as a pigment, 4.0 parts by weight of BYK-2001(BYK corporation) as a pigment dispersant, and 66 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed, and the pigment was sufficiently dispersed by a ball mill.
Examples 1 to 6 and comparative examples 1 to 4: production of colored photosensitive resin composition
Example 1.
A colored photosensitive resin composition was prepared by mixing 15.869 wt% of the alkali-soluble resin (A-1) of the synthetic example, 4.015 wt% of dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon chemical) as the photopolymerizable compound (B), 0.964 wt% of C-1 of Table 1 below as the photopolymerization initiator, 4.5 wt% of the pigment dispersion composition (D) of the production example, 17 wt% of ethyl 3-ethoxypropionate (E-1) as the solvent, 57.646 wt% of propylene glycol monomethyl ether acetate (E-2), and 0.006 wt% of polyether-modified silicone oil (SH8400, Toray silicone (Ltd.) as the additive.
Examples 2 to 6.
Colored photosensitive resin compositions were produced by the same method as in example 1, using the components and contents shown in table 1 below.
Comparative examples 1 to 4.
Colored photosensitive resin compositions were produced by the same method as in example 1, using the components and contents shown in table 1 below.
[ Table 1]
Figure BDA0001400519410000221
Example of production of color Filter
The colored photosensitive resin compositions of examples 1 to 6 and comparative examples 1 to 4 were applied onto a glass substrate (Corning Corp.) having a size of 5X 5cm by spin coating, and then placed on a hot plate and maintained at a temperature of 100 ℃ for 3 minutes to form a film having a thickness of 3.0. mu.mA film. Then, a test photomask having a pattern in which the transmittance is changed in a stepwise manner within a range of 1 to 100% and a line/space pattern of 1 μm to 100 μm was placed on the film, and the film was irradiated with ultraviolet light with the interval from the test photomask set to 100 μm. In this case, a high pressure mercury lamp of 1kw including all g, h and I rays was used as the ultraviolet light source, and the lamp was set at 100mJ/cm2The illumination of (2) is performed without using a special optical filter. The film irradiated with ultraviolet light was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes to be developed. After the glass plate coated with the above film was washed with distilled water, it was dried by blowing nitrogen gas and heated in a heating oven at 200 ℃ for 30 minutes. The pattern shape (film) thickness of the color filter thus obtained was 3 μm.
Experimental example 1: development speed, sensitivity, pattern stability, cone linewidth experiment
1) Developing speed: the time required for the non-exposed portion to be first dissolved in the Developer during development (Spray Developer) HPMJ method) was measured, and the results are shown in table 2 below.
2) Sensitivity: the minimum exposure amount required for forming a peeled film having no pattern after development was measured, and the results are shown in table 2 below.
3) Pattern stability: the degree of pattern errors (degree of pattern peeling, linearity failure, etc.) after exposure using a pattern mask at a low exposure dose (20 to 100mJ) was measured. The pattern stability was evaluated in accordance with the following criteria, and the results are shown in table 2 below. At this time, the error in the pattern was confirmed by an optical microscope (ECLIPSE LV100POL Model 100, manufactured by nikon corporation) of a three-dimensional surface topography instrument.
O: no error or less than 3 on the pattern
X: there are more than 3 errors on the pattern
4) Cone line width: after forming a pattern having a lateral length of 100 μm by exposure using a pattern mask, the obtained cured film was observed by a scanning electron microscope (manufactured by S-4600, hitachi corporation) and the line width of the pattern was measured, and the results are shown in table 2 below.
[ Table 2]
Figure BDA0001400519410000241
Referring to table 2 above, in the case where both the alkali-soluble resin of the present invention and the photopolymerization initiator were contained (examples 1 to 6), improvement in sensitivity and pattern stability was confirmed as compared with the case where the alkali-soluble resin of the present invention and the photopolymerization initiator were not contained (comparative examples 1 to 2), and particularly, improvement in cone line width was also confirmed as compared with comparative example 1 described above, improvement in sensitivity and pattern stability was confirmed as compared with the case where the photopolymerization initiator of the present invention was not contained (comparative example 3), and improvement in development speed, sensitivity, pattern stability, and cone line width was confirmed as compared with the case where the alkali-soluble resin of the present invention was not contained (comparative example 4).
Experimental example 2: experiment for confirming hardness, solvent resistance, heat resistance and change in brightness before/after heat resistance
1) Pencil hardness: pencil hardness test was carried out in accordance with JIS K5600-5-4, and the results are shown in Table 3 below.
2) Solvent resistance: the color change (. DELTA.E. ab) was measured by immersing the substrate in N-methyl-2-pyrrolidone (NMP) solvent at 23 ℃ for 30 minutes. In this case, the measurement apparatus used a microspectrophotometer (model No. osp-SP2000, olympus corporation), and CIE color coordinate values before and after solvent resistance evaluation were measured by the apparatus, and the degree of color change was confirmed by the following equation 1, and the results are shown in table 3 below.
[ mathematical formula 1]
△E*ab＝[(△L*)2+(△a*)2+(△b*)2]1/2
○：△E*ab<1
△：1≤△E*ab≤3
×：△Eab>3
3) Heat resistance and heat resistance change in luminance (Δ Y) before/after evaluation: after heating the color filter manufactured in the manufacturing example of the present invention in a heating oven at 230 ℃ for 2 hours, the color change before/after heating was calculated by the above mathematical formula 1, and the change in luminance before/after heat resistance evaluation was confirmed by a microspic Spectrophotometer (model No. osp-SP2000, olympus corporation) to confirm whether or not there was a decrease in luminance due to thermal yellowing. The heat resistance evaluation criteria are the same as the above solvent resistance, and the brightness change criteria are described below. The experimental results are shown in table 3 below.
○：-0.04≤△Y≤0.00
×：-0.04＞△Y
[ Table 3]
Figure BDA0001400519410000251
Referring to table 3 above, when the case where both the alkali-soluble resin of the present invention and the photopolymerization initiator were contained (examples 1 to 6) was compared with the case where the alkali-soluble resin of the present invention and the photopolymerization initiator were not contained (comparative examples 1 to 2), the case where the photopolymerization initiator of the present invention was not contained (comparative example 3), and the case where the alkali-soluble resin of the present invention was not contained (comparative example 4), it was confirmed that all of the hardness, solvent resistance, heat resistance, and luminance change were improved.
Experimental example 3 test on the size and shape of contact hole, resistance to stripping liquid and IZO etching liquid
The negative PR (Photoresist) of examples 1 to 6 and comparative examples 1 to 4 was coated on the R/G/B pattern coating film, and then placed on a hot plate and maintained at a temperature of 90 ℃ for 1 minute to form a thin film. Then, a test photomask having a pattern in which the transmittance is changed in a stepwise manner within a range of 1 to 100% and a line/space pattern of 1 to 50 μm is placed on the film, and the film is irradiated with ultraviolet light with the interval from the test photomask set to 100 μm. In this case, a high pressure mercury lamp of 1kw including all g, h, and i lines was used as the ultraviolet light source, and the lamp was set at 100mJ/cm2The illumination of (2) is performed without using a special optical filter. The film irradiated with the ultraviolet rays is again placed on the hot plate at 1The film was further cured by maintaining the temperature at 10 ℃ for 1 minute. The film irradiated with the ultraviolet ray was immersed in a developing solution of TMAH 2.38% aqueous solution for 30 seconds to be developed. The glass plate coated with the film was washed with distilled water, then dried by blowing nitrogen gas, and heated in a heating oven at 130 ℃ for 2 minutes. The negative PR pattern shape (film) thus obtained was 3 μm thick. The deposition conditions for the IZO thin film were determined by a sputtering machine (Sputter),
Figure BDA0001400519410000262
is suitable, more preferably
Figure BDA0001400519410000263
Degree of the disease. The criteria for each experiment are as follows, and the results are shown in table 4 below.
1) The size of the contact hole: diameter of Contact Hole after exposure of 40 μm pattern of Contact Hole Mask (Contact Hole Mask)
2) Shape of the contact hole: after exposure of a 40 μm square pattern of a contact hole mask, the degree of expression of the 40 μm mask pattern on an SEM (S-4300, manufactured by Hitachi Ltd.) image
In this case, the degree of expression is expressed by% as the degree of coincidence between the diameter of the contact hole after exposure and the diameter of the contact hole mask, and the degree of coincidence is approximately 100%.
3) Resistance to stripping liquid and IZO etching liquid: the same procedures as those for the Spray Developer (HPMJ method) were carried out using a stripping liquid (PRS-2000, Dongyou Fine chemical), an IZO etching liquid (MA-S03/MASZ02, Dongyou fine chemical). The stability of the coating film by IZO etching liquid was confirmed by immersing the substrate in IZO etching conditions at 35 ℃ for 2 minutes and then washing the substrate with water, and the conditions of the stripping liquid were evaluated for about 4 minutes under temperature conditions adjusted to a range of 70 to 80 ℃. The stability of the coating film was also confirmed by evaluation of the stripping liquid. Specifically, in the evaluation of the resistance to the stripping liquid and IZO etching liquid, the degree of pattern errors after exposure of the 100 μm pattern of the pattern mask was evaluated, the pattern errors were confirmed by an optical microscope of a three-dimensional topographer, and the results were evaluated according to the following criteria and are shown in table 4 below.
O: 1-3 errors on the pattern
X: more than 3 dislocations in the pattern and pattern peeling
[ Table 4]
Figure BDA0001400519410000261
Referring to table 4 above, it was confirmed that the contact hole size, shape, peeling liquid resistance and IZO etching liquid resistance were improved when the cases (examples 1 to 6) including both the alkali-soluble resin of the present invention and the photopolymerization initiator, and the cases (comparative examples 1 to 2) not including the alkali-soluble resin of the present invention and the photopolymerization initiator (comparative example 3) not including the photopolymerization initiator, and the contact hole shape, peeling liquid resistance and IZO etching liquid resistance were improved when the cases (comparative example 4) not including the alkali-soluble resin of the present invention.
Experimental example 4: degassing measurement experiment
The color filter produced in the above production example was thermally decomposed at 230 ℃ for 30 minutes by Py-GC/FID, and the trapped compound was analyzed for the following evaluation criteria.
The degassing value of comparative example 1 is represented by a percentage based on 100%, and the smaller the value, the better the degassing value. The results are shown in table 5 below.
[ Table 5]
Figure BDA0001400519410000271
Referring to table 5 above, when the cases (examples 1 to 6) including both the alkali-soluble resin of the present invention and the photopolymerization initiator were compared with the cases (comparative examples 1 to 2) not including the alkali-soluble resin of the present invention and the photopolymerization initiator, the cases (comparative example 3) not including the photopolymerization initiator of the present invention, and the cases (comparative example 4) not including the alkali-soluble resin of the present invention, it was confirmed that the degassing (%) phenomenon was improved.

Claims (5)

1. Use of a colored photosensitive resin composition for forming a color filter on an array in which the coincidence degree of the diameter of a contact hole and the diameter of a contact hole mask used at the time of exposure of the contact hole is 90% or more, the colored photosensitive resin composition comprising an alkali-soluble resin containing a repeating unit represented by the following chemical formula 1, and a photopolymerization initiator containing one or more compounds selected from the group consisting of compounds represented by the following chemical formula 2:
chemical formula 1
Figure FDA0003058073010000011
In the chemical formula 1, the metal oxide is represented by,
R1and R2Each independently a hydrogen atom or a methyl group,
R3is a residue containing a carboxylic acid derived from an acid anhydride,
chemical formula 2
Figure FDA0003058073010000012
In the chemical formula 2, the first and second organic solvents,
R4～R13each independently of the others is hydrogen, halogen, C1～C20Alkyl of (C)6～C20Aryl of (C)1～C20Alkoxy group of (C)7～C40Arylalkyl of C1～C20Hydroxyalkyl of (C)2～C40Hydroxyalkoxyalkyl or C3～C20A cycloalkyl group of (a).
2. The use according to claim 1, wherein the content of the repeating unit represented by the chemical formula 1 is 50 to 90 mol% with respect to the total mol% of the alkali-soluble resin.
3. The use according to claim 1, wherein the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight based on the total weight of solid components in the colored photosensitive resin composition.
4. The use according to claim 1, wherein the colored photosensitive resin composition further comprises one or more selected from the group consisting of a photopolymerizable compound, a colorant, a solvent, and an additive.
5. Use according to claim 1, the colour filter being applied in an image display device.
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