KR20140081463A - Photosensitive resin composition and light blocking layer using the same - Google Patents
Photosensitive resin composition and light blocking layer using the same Download PDFInfo
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- KR20140081463A KR20140081463A KR1020120151246A KR20120151246A KR20140081463A KR 20140081463 A KR20140081463 A KR 20140081463A KR 1020120151246 A KR1020120151246 A KR 1020120151246A KR 20120151246 A KR20120151246 A KR 20120151246A KR 20140081463 A KR20140081463 A KR 20140081463A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- 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
- G02F1/133512—Light shielding layers, e.g. black matrix
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Abstract
Description
The present invention relates to a photosensitive resin composition and a light-shielding layer using the same.
A liquid crystal display device includes a lower substrate on which a color filter including a light shielding layer and an ITO pixel electrode are formed; An active circuit composed of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer; And an upper substrate on which ITO pixel electrodes are formed.
The light-shielding layer serves to cut off light which is transmitted through the substrate other than the transparent pixel electrode in order to prevent the contrast caused by the light transmitted through the thin film transistor from deteriorating, and the colored layers of red, green, The main role is to transmit light of a specific wavelength to express color.
Recent development trends of shading layers have focused on multifunctional materials, one of which is to have two functions simultaneously in one process. For example, in one process, a black matrix and a column spacer are simultaneously realized as one material, and the thus formed portion is called a black column spacer.
The black column spacer may also implement the black matrix and column spacer in one pattern. At this time, pattern formation is required to use a half tone mask or a slit mask in the pattern formation process so that a difference in film thickness appears between the exposed part and the less exposed part.
One embodiment of the present invention is to provide a photosensitive resin composition which is capable of controlling film steps as well as being excellent in pattern forming property, developability and chemical resistance.
Another embodiment of the present invention is to provide a light-shielding layer made using the photosensitive resin composition.
One embodiment of the present invention is a resin composition comprising: (A) a binder resin comprising a cardo-based resin containing a repeating unit represented by the following formula (1); (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.
[Chemical Formula 1]
(In the
Y 1 is an acid anhydride residue,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, at least one of R 1 and R 2 is the substituted or unsubstituted (meth) acrylate group,
R 3 to R 6 are each independently a substituted or
a 1 to a 4 each are an integer of 0 to 4,
b 1 and b 2 are each an integer of 0 to 10).
The catadiene resin may be a compound represented by the following general formula (2).
(2)
(In the formula (2)
Y < 2 > is an acid anhydride residue,
Z 1 and Z 2 are each an acid anhydride residue,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 7 and R 8 is the substituted or unsubstituted (meth) acrylate group,
R 9 to R 12 and R 15 to R 18 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 To C30 aryl group,
a 5 to a 12 are each an integer of 0 to 4,
b 3 to b 6 each represent an integer of 0 to 10,
and n < 1 > is an integer of 1 to 20.)
The cadmium resin may further comprise a repeating unit represented by the following formula (4).
[Chemical Formula 4]
(In the formula 4,
Y < 3 > is an acid anhydride residue,
R 19 to R 22 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 13 to a 16 each is an integer of 0 to 4,
b 7 and b 8 are each an integer of 0 to 10).
The cardade resin may be a compound represented by the following general formula (5).
[Chemical Formula 5]
(In the above formula (5)
Y 4 and Y 5 are each an acid anhydride residue,
Z 3 and Z 4 are each an acid anhydride residue,
R 23 and R 24 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 23 and R 24 is the substituted or unsubstituted (meth) acrylate group,
R 25 to R 36 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 17 to a 28 are each an integer of 0 to 4,
b 9 to b 14 each are an integer of 0 to 10,
n 2 and n 3 are each an integer of 1 to 10.)
The cardade resin may have a weight average molecular weight of 1,000 to 20,000 g / mol.
The colorant may comprise a dye, a pigment or a combination thereof.
The pigment may comprise an organic pigment, an inorganic pigment or a combination thereof, and the organic pigment may include a black organic pigment, and the inorganic pigment may include carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, aniline Black, or a combination thereof.
The photosensitive resin composition comprises (A) 5 to 30% by weight of the binder resin; (B) 1 to 20% by weight of the photopolymerizable monomer; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 1 to 50% by weight of the colorant; And (E) the solvent balance.
Another embodiment of the present invention provides a light-shielding layer produced using the photosensitive resin composition.
Other details of the embodiments of the present invention are included in the following detailed description.
It is possible to realize a light-shielding layer which is excellent in pattern forming property, developability and chemical resistance and has a film step.
FIG. 1 is a schematic view showing one form of a mask used for pattern formation in manufacturing a light-shielding layer according to one embodiment.
2 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Example 1. Fig.
3 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Comparative Example 4. Fig.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.
"Hetero" means that at least one C atom in a ring substituent is substituted with at least one heteroatom selected from N, O, S, and P, unless otherwise specified herein.
&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.
The photosensitive resin composition according to one embodiment may comprise (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a colorant and (E) a solvent.
Each component will be described in detail below.
(A) Binder resin
In one embodiment, a cardboard resin can be used as the binder resin. The cation resin may be a compound containing a repeating unit represented by the following formula (1).
[Chemical Formula 1]
(In the
Y 1 is an acid anhydride residue,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, at least one of R 1 and R 2 is the substituted or unsubstituted (meth) acrylate group,
R 3 to R 6 are each independently a substituted or
a 1 to a 4 each are an integer of 0 to 4,
b 1 and b 2 are each an integer of 0 to 10).
When the cation resin is used, the heat resistance, chemical resistance and adhesion of the photosensitive resin composition can be improved.
In addition, the cardade resin according to one embodiment has a spirobifluorene skeleton as in the above formula (1). The spirobifluorene skeleton has a stable three-dimensional structure and a high rigidity structure. As a result of using such a cadene resin, the melting characteristic during post-baking in the pattern formation process is lowered, and the film step of the pattern after development can be maintained as it is. In other words, the carded resin according to one embodiment can form a pattern having a film step and an excellent pattern forming property when used in the photosensitive resin composition due to the low fluidity.
The cadmium resin may include at least one (meth) acrylate group as shown in
In addition, since the cado resin is synthesized by introducing the (meth) acrylate group in the final step after synthesis of a polymer containing an acid dianhydride moiety substituted with a carboxyl group, the substituent of the (meth) acrylate group can be controlled. Accordingly, it is possible to control the melting characteristic and the sensitivity due to the rigid structure.
The cardo resin containing the repeating unit represented by the formula (1) may specifically be a compound represented by the following formula (2).
(2)
(In the formula (2)
Y < 2 > is an acid anhydride residue,
Z 1 and Z 2 are each an acid anhydride residue,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 7 and R 8 is the substituted or unsubstituted (meth) acrylate group,
R 9 to R 12 and R 15 to R 18 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 To C30 aryl group,
a 5 to a 12 are each an integer of 0 to 4,
b 3 to b 6 each represent an integer of 0 to 10,
and n < 1 > is an integer of 1 to 20.)
The cation resin may be more specifically a compound represented by the following formula (3).
(3)
(In the above formula (3), n 4 is an integer of 1 to 20)
In addition to the repeating unit represented by
[Chemical Formula 4]
(In the formula 4,
Y < 3 > is an acid anhydride residue,
R 19 to R 22 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 13 to a 16 each is an integer of 0 to 4,
b 7 and b 8 are each an integer of 0 to 10).
The cation resin including the repeating unit represented by the formula (1) and the repeating unit represented by the formula (4) may be a compound represented by the following formula (5).
[Chemical Formula 5]
(In the above formula (5)
Y 4 and Y 5 are each an acid anhydride residue,
Z 3 and Z 4 are each an acid anhydride residue,
R 23 and R 24 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 23 and R 24 is the substituted or unsubstituted (meth) acrylate group,
R 25 to R 36 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 17 to a 28 are each an integer of 0 to 4,
b 9 to b 14 each are an integer of 0 to 10,
n 2 and n 3 are each an integer of 1 to 10.)
The cation resin may be more specifically a compound represented by the following formula (6).
[Chemical Formula 6]
(In the above formula (6), n 5 and n 6 are each an integer of 1 to 10)
The cadene resin may have a weight average molecular weight of 1,000 to 20,000 g / mol, and more specifically, a weight average molecular weight of 3,000 to 10,000 g / mol. When the weight average molecular weight is within the above range, excellent patterning property and developability can be obtained when the light shielding layer is formed.
As the binder resin, an acrylic resin may be used together with the above-mentioned cation resin.
The acrylic resin may contain a first ethylenic unsaturated monomer And a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
The first ethylenically unsaturated monomer may be contained in an amount of 5 to 50% by weight, and more specifically 10 to 40% by weight based on the total amount of the acrylic resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.
Specific examples of the acrylic resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer , Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.
The weight average molecular weight of the acrylic resin may be 3,000 to 150,000 g / mol, specifically 5,000 to 50,000 g / mol, and more specifically 2,000 to 30,000 g / mol. When the weight average molecular weight of the acrylic resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion with a substrate during the production of a light-shielding layer.
The acid value of the acrylic resin may be 15 to 60 mgKOH / g, and specifically 20 to 50 mgKOH / g. When the acid value of the acrylic resin is within the above range, the resolution of the pixel pattern is excellent.
The binder resin may be added to the total amount of the photosensitive resin composition 5 to 30% by weight, and more specifically, 7 to 25% by weight. When the binder resin is contained within the above range, the viscosity is appropriately maintained, and the patterning property, the processability, and the developing property are excellent when the light-shielding layer is produced.
(B) Photopolymerization Monomer
The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.
Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.
Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.
A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ®, the same M-111 ®, the same M-114 ®; KAYARAD TC-110S ® and TC-120S ® from Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of V-158 ®, V-2311 ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ®, copper or the like M-240 ®, the same M-6200 ®; KAYARAD HDDA ® , HX-220 ® and R-604 ® from Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of 社V-260 ®, V- 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ®, the same M-400 ®, the same M-405 ®, the same M-450 ®, Dong M -7100 ® , copper M-8030 ® , copper M-8060 ® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ®, copper DPCA-20 ®, ® copper -30, -60 ® copper, copper ® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ®, copper ® -300, -360 ® copper, copper -GPT ®, copper -3PA ®, and the like copper -400 ®. These products may be used alone or in combination of two or more.
The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.
The photopolymerizable monomer may be contained in an amount of 1 to 20% by weight based on the total amount of the photosensitive resin composition, and specifically 1 to 15% by weight. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in sensitivity in the presence of oxygen, and is excellent in compatibility with the binder resin.
(C) Light curing Initiator
The photopolymerization initiator may be, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, or a triazine-based compound as a photopolymerization initiator generally used in a photosensitive resin composition.
Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-crothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, Propyl thioxanthone, 2-chlorothioxanthone, and the like.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine.
The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, or a nonimidazole compound in addition to the above compounds.
The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy .
The photopolymerization initiator may be contained in an amount of 0.1 to 10% by weight based on the total amount of the photosensitive resin composition, specifically 0.5 to 3% by weight. When the photopolymerization initiator is contained within the above range, the sensitivity of the radical is good, the color density of the photosensitive resin composition solution is appropriately maintained, and the decrease of the transmittance due to the unreacted initiator can be prevented.
(D) Colorant
The colorant may be a pigment, a dye, or a combination thereof.
The pigment may be an organic pigment, an inorganic pigment or a combination thereof. Among them, the organic pigments and the inorganic pigments may be mixed and used for better optical density.
The organic pigments may be black organic pigments. The black organic pigment is insulating.
Examples of the black organic pigments include perylene black and cyanine black, which may be used alone or in combination of two or more.
The black organic pigment may also be a mixture of two or more kinds of organic pigments and having a black color. Specific examples of the pigments include a red pigment, a blue pigment, a green pigment, a violet pigment, a yellow pigment, a cyanine pigment, and a magenta pigment (Margenta) ) Based pigments may be combined and blackened. For example, a red pigment, a blue pigment and a green pigment may be mixed and blackened, or a green pigment and a violet pigment may be mixed and blackened.
Examples of the red pigments include perylene pigments, anthraquinone pigments, giant anthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. have. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, siccone pigments, anthraquinone (sudan I, II, III, R), giant anthraquinone , Vis azo, benzopyran and the like.
Examples of the blue pigments include metal phthalocyanine pigments, indanthrone pigments, indophenol pigments, and the like. Specific examples of the blue pigments include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloroal phthalocyanine, titanyl phthalocyanine, vanadinic phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine and cobalt phthalocyanine.
As the green pigments, halogenated phthalocyanine pigments And the like. Specific examples thereof include porichlorol copper phthalocyanine, poricholol bromo phthalocyanine, and the like.
Examples of the violet pigment include GeoKi Photo Violet Sat, First Violet B, Methyl Violet Toyoki, Indanthrene Violet Rain Violet and the like.
Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Specific examples thereof include hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR), and anthracene.
Examples of the cyanine pigment include metal-free phthalocyanine, merocyanine, and the like.
Examples of the margenta pigment include dimethyl quinacridone, thioindigo, and the like.
Examples of the inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, and aniline black. These inorganic pigments exhibit high resistance characteristics, and they can be used singly or in combination of two or more kinds.
The organic pigment and the inorganic pigment may be mixed in a weight ratio of 1 to 10: 1, and may be used in a weight ratio of 2 to 7: 1. When mixed in the weight ratio range, the processability is stable and the dielectric constant can be low.
A dispersant may be used together to disperse the pigment well in the photosensitive resin composition.
The dispersant may be added to the inside of the pigment in the form of surface-treating the pigment in advance, or may be used in the production of the photosensitive resin composition together with the pigment.
The dye may be a triphenylmethane-based dye, an anthraquinone-based dye, an azo-based dye or a combination thereof. Among them, the triphenylmethane-based dye, at least one of the anthraquinone-based dye and the azo-based dye Can be mixed and used.
The colorant may be contained in an amount of 1 to 50% by weight based on the total amount of the photosensitive resin composition, specifically 5 to 45% by weight. When the colorant is contained within the above range, excellent insulating property, high optical density can be obtained, and excellent processability such as developability can be obtained.
(E) Solvent
Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether and propylene glycol monomethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.
In view of miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol dimethyl ether are preferred; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be included in an amount of 30% to 70% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity and is excellent in processability.
(F) Other additives
The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent stains and spots upon application, to prevent leveling, 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And other additives such as a radical polymerization initiator.
Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.
Examples of the fluorine-based surfactant, BM Chemie Corporation BM-1000 ®, BM-1100 ® , and the like; Mecha Pack F 142D ® , Copper F 172 ® , Copper F 173 ® , Copper F 183 ® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ®, the same FC-170C ®, copper FC-430 ®, the same FC-431 ®, and the like; Asahi Grass Co., Inc. Saffron S-112 ®, the same S-113 ®, the same S-131 ®, the same S-141 ®, the same S-145 ®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ®, ® -190 copper, may be a commercially available product such as copper -193 ®, SZ-6032 ®, SF-8428 ®.
The additive can be easily adjusted according to desired properties.
Another embodiment provides a light-shielding layer made using the above-described photosensitive resin composition.
The method of manufacturing the light-shielding layer is as follows.
(1) Coating and Film Formation Step
The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate to a desired thickness, for example, a thickness of 0.5 to 25 占 퐉, by using a spin or slit coat method, a roll coating method, a screen printing method or an applicator method And then the solvent is removed by heating at a temperature of 70 to 110 DEG C for 1 to 10 minutes to form a coating film.
(2) Exposure step
In order to form a pattern necessary for the obtained coating film, a mask of a predetermined type is interposed, and an active line of 190 to 500 nm is irradiated.
The mask can be used in various forms, specifically, in the form shown in FIG.
FIG. 1 is a schematic view showing one form of a mask used for pattern formation in manufacturing a light-shielding layer according to one embodiment.
Figure 1 shows a mask with a 100% shielded area, a 100% transparent area, and a 10 to 90% transparent area. In FIG. 1, the region which is 10 to 90% transmissive may have a half tone or a slit shape. By using the mask of the above-described type, it is possible to form a film step between the exposed part and the less exposed part. Specifically, a portion that is 100% exposed through a 100% transparent region of the mask may form a column spacer, and a portion exposed through a 10 to 90% transparent region of the mask may form a black matrix . Thus, a step can be generated in the forming portion of the black matrix.
As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.
The exposure dose varies depending on the kind of each component of the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high pressure mercury lamp is used, the exposure dose is 500 mJ / cm 2 (By a 365 nm sensor).
(3) Development step
Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.
(4) Post-treatment step
The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.
By using the above-mentioned photosensitive resin composition, excellent adhesion and optical density required for the light-shielding layer can be obtained.
When the exposure and development steps are performed during the pattern formation process, a film step is formed between a region exposed by the use of a halftone mask or a slit mask and a region exposed to less exposure, and after the post-baking process, The formed film step can be maintained due to the reduced melting property of the photosensitive resin composition according to the embodiment. Also, according to one embodiment, the portion where the stepped black matrix is formed may undergo a crosslinking reaction as in the case of 100% exposed portions, so that the chemical resistance to the solvent may be improved. Specifically, the chemical resistance of the light-shielding layer material is excellent with respect to the main solvent constituting the alignment layer formed on the light-shielding layer when forming the LCD panel, for example, N-methylpyrrolidone. Accordingly, a black column spacer functioning as a black matrix and a column spacer can be implemented concretely.
Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.
Manufacturing example One: Carometer Resin Manufacturing
(1) In a 1 L reactor, 50 g of 9,9'-spirobifluorene (TCI) and 500 ml of carbon disulfide (CS 2 ) (Aldrich) were placed and heated to 45 ° C. 31 g of acetyl chloride (Aldrich) Chloride (Aldrich), and the mixture was stirred for 10 hours. After completion of the reaction, the carbon disulfide was distilled off under reduced pressure, and 500 ml of dichloromethane and 300 ml of water were added thereto. The mixture was stirred at room temperature for 2 hours, and then the organic layer was taken and vacuum distillation was conducted to obtain a compound represented by the following formula (7).
(7)
(2) In a 1 L reactor, 60 g of the compound represented by the above formula (7) and 40 g of meta-chloroperoxybenzoic acid (Aldrich) were placed, 500 ml of dichloromethane was added, and the mixture was heated to 43 캜 and stirred for 8 hours. After stirring at room temperature for 30 minutes, the organic layer was taken and distilled under reduced pressure to obtain a compound represented by the formula (8) through a silica gel column.
[Chemical Formula 8]
(3) A 500 ml reactor was charged with 50 g of the compound represented by the formula (8), 300 ml of methanol (Aldrich) and 200 ml of 6N NaOH aqueous solution, stirred at room temperature for 20 hours, distilled under reduced pressure, The mixture was extracted with an organic layer using 500 ml of dichloromethane, and the organic layer was taken and distilled under reduced pressure to obtain a compound represented by the following formula (9) through a silica gel column.
[Chemical Formula 9]
(4) A 500 ml reactor was charged with 50 g of the compound represented by the formula 9, 24 g of 2-hydroxyethyl chloride (Aldrich), 60 g of potassium carbonate (anhydrous) (Aldrich) and 300 g of dimethylformamide (Aldrich) And the mixture was stirred for 6 hours. After cooling, the reaction solution was poured into 2 L of water for 1 hour to precipitate crystals. The crystals were precipitated, filtered and washed, and dried in a vacuum oven at 50 ° C for 12 hours to obtain a compound ≪ / RTI >
[Chemical formula 10]
(5) In a 1 L reactor, 50 g of the compound represented by the formula (10), 18.5 g of biphenyltetracarboxylic dianhydride (Aldrich), 7.1 g of tetrahydrophthalic anhydride (Aldrich) and 0.5 g of tetramethylammonium chloride were added to propylene glycol methyl ether Acetate, and the mixture was stirred at 120 DEG C for 6 hours to obtain a copolymer having a solid content of 49.3% by weight, an acid value of 132 mgKOH / g and a weight average molecular weight 4,800 g / mol of a compound represented by the following formula (11) was obtained.
(11)
(6) In a 1 L reactor, 4.3 g of glycidyl methacrylate (Aldrich), 2.5 g of tetrahydrophthalic anhydride (Aldrich) and 0.5 g of tetramethylammonium chloride were added to the reaction solution containing the compound represented by Formula 11 And the mixture was stirred at 120 ° C for 6 hours to prepare a camoid resin represented by the following formula (6) with a solid content of 39.3% by weight and a weight average molecular weight of 4,900 g / mol.
[Chemical Formula 6]
(Preparation of photosensitive resin composition)
The specifications of the components used in the production of the photosensitive resin composition are as follows
(A) Binder resin
(A-1) The cardade resin prepared in Production Example 1 was used.
(A-2) V259ME from Shinil Chemical Co., Ltd., having a solid content of 55% by weight, was used.
(A-3) Wako CF-61 having a solid content of 32% by weight was used.
(B) Photopolymerization Monomer
Dipentaerythritol hexaacrylate was used.
(C) Light curing Initiator
(C-1) OXE02 from Shiba Co., Ltd. was used.
(C-2) Shiga-Kagi's IGR907 was used.
(D) Colorant
(D-1) A pigment dispersion (MICHONY, TCZ-121) containing a pigment of red, blue and violet as a main component was used.
(D-2) A pigment dispersion (TCZ-180, Michikini Co., Ltd.) dispersed with an organic black pigment was used.
(D-3) A pigment dispersion containing carbon black (Sakata Corporation, Cl-M-050) was used.
(E) Solvent
Propylene glycol monomethyl ether acetate was used.
(F) Additive
(F-1) As the surfactant, F-475 manufactured by DIC was used.
(F-2) Aminopropyltrimethoxysilane (S-710 from Chisso) was used as the silane coupling agent.
Example 1 to 3 and Comparative Example 1 to 4
Each component was mixed with the composition shown in Table 1 below to prepare a photosensitive resin composition. Specifically, the photopolymerization initiator was dissolved in the solvent, followed by sufficient stirring at room temperature for about 30 minutes. The binder resin and the photopolymerizable monomer were added thereto, followed by stirring for 1 hour. The additive was added thereto, a colorant was added, and the mixture was stirred for about 2 hours. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.
Rating 1: Pattern Formability And Developability Measure
The photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were placed on a glass substrate And dried to form a coating film. Each coating was irradiated with 70 mJ / cm 2 of light having a wavelength of 365 nm by using a mask as shown in Fig. Developed in an aqueous solution diluted with 1% by weight of potassium hydroxide at 23 DEG C for 1 minute, then rinsed with pure water for 1 minute. The pattern obtained by this method was cured by heating in an oven at 220 캜 for 30 minutes, and then the shape of the pattern was visually observed using an optical microscope. The results are shown in Table 2 and Figs. 2 and 3.
FIG. 2 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Example 1, and FIG. 3 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Comparative Example 4. FIG.
<Evaluation Criteria of Pattern Formability>
Good: Formability of 10 mu m pattern is good
DELTA: poor formability of 10 mu m pattern
×: No formation of 10 μm pattern
≪ Development evaluation standard &
○: The coating gradually develops
X: Developed as if the coating was torn
Evaluation 2: Chemical resistance measurement
Each of the pattern samples according to Examples 1 to 3 and Comparative Examples 1 to 4 obtained in
<Evaluation criteria for chemical resistance>
○: No color change at all
?: 20% or less color change (100% color change when opaque)
×: 20% or more color change (100% color change when opaque)
Through the above Table 2, it can be seen that the patternability, developability and chemical resistance of both Examples 1 to 3 were superior to those of Comparative Examples 1 to 4, in which cadmium resin according to one embodiment was used as a binder resin .
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (9)
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant; And
(E) Solvent
.
[Chemical Formula 1]
(In the formula 1,
Y 1 is an acid anhydride residue,
R 1 and R 2 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, at least one of R 1 and R 2 is the substituted or unsubstituted (meth) acrylate group,
R 3 to R 6 are each independently a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 alkynyl group, a substituted or unsubstituted C 1 to C 20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 1 to a 4 each are an integer of 0 to 4,
b 1 and b 2 are each an integer of 0 to 10).
Wherein the cation resin is a compound represented by the following formula (2).
(2)
(In the formula (2)
Y < 2 > is an acid anhydride residue,
Z 1 and Z 2 are each an acid anhydride residue,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 7 and R 8 is the substituted or unsubstituted (meth) acrylate group,
R 9 to R 12 and R 15 to R 18 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 To C30 aryl group,
a 5 to a 12 are each an integer of 0 to 4,
b 3 to b 6 each represent an integer of 0 to 10,
and n < 1 > is an integer of 1 to 20.)
Wherein the cadoptic resin further comprises a repeating unit represented by the following formula (4).
[Chemical Formula 4]
(In the formula 4,
Y < 3 > is an acid anhydride residue,
R 19 to R 22 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 13 to a 16 each is an integer of 0 to 4,
b 7 and b 8 are each an integer of 0 to 10).
Wherein the cado-based resin is a compound represented by the following formula (5).
[Chemical Formula 5]
(In the above formula (5)
Y 4 and Y 5 are each an acid anhydride residue,
Z 3 and Z 4 are each an acid anhydride residue,
R 23 and R 24 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group , Or a substituted or unsubstituted (meth) acrylate group, and at least one of R 23 and R 24 is the substituted or unsubstituted (meth) acrylate group,
R 25 to R 36 each independently represent a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a 17 to a 28 are each an integer of 0 to 4,
b 9 to b 14 each are an integer of 0 to 10,
n 2 and n 3 are each an integer of 1 to 10.)
Wherein the cation resin has a weight average molecular weight of 1,000 to 20,000 g / mol.
Wherein the colorant comprises a dye, a pigment, or a combination thereof.
The pigment comprises an organic pigment, an inorganic pigment or a combination thereof,
Wherein the organic pigment comprises a black organic pigment,
Wherein the inorganic pigment includes carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, aniline black, or a combination thereof.
The photosensitive resin composition
(A) 5 to 30% by weight of the binder resin;
(B) 1 to 20% by weight of the photopolymerizable monomer;
(C) 0.1 to 10% by weight of the photopolymerization initiator;
(D) 1 to 50% by weight of the colorant; And
(E) the solvent remaining amount
.
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| KR1020120151246A KR20140081463A (en) | 2012-12-21 | 2012-12-21 | Photosensitive resin composition and light blocking layer using the same |
| CN201310306404.9A CN103885291A (en) | 2012-12-21 | 2013-07-19 | Photosensitive resin composition and light blocking layer using the same |
| US13/947,232 US8834749B2 (en) | 2012-12-21 | 2013-07-22 | Photosensitive resin composition and light blocking layer using the same |
| TW102126484A TWI509359B (en) | 2012-12-21 | 2013-07-24 | Photosensitive resin composition and light blocking layer using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180080507A (en) * | 2017-01-04 | 2018-07-12 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and display device |
| KR20180094655A (en) * | 2017-02-16 | 2018-08-24 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
-
2012
- 2012-12-21 KR KR1020120151246A patent/KR20140081463A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180080507A (en) * | 2017-01-04 | 2018-07-12 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and display device |
| KR20180094655A (en) * | 2017-02-16 | 2018-08-24 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
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