KR101895309B1 - Photosensitive resin composition, photosensitive resin layer and color filter comprising the same - Google Patents
Photosensitive resin composition, photosensitive resin layer and color filter comprising the same Download PDFInfo
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- KR101895309B1 KR101895309B1 KR1020160008752A KR20160008752A KR101895309B1 KR 101895309 B1 KR101895309 B1 KR 101895309B1 KR 1020160008752 A KR1020160008752 A KR 1020160008752A KR 20160008752 A KR20160008752 A KR 20160008752A KR 101895309 B1 KR101895309 B1 KR 101895309B1
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- photosensitive resin
- weight
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- OFEGXVATUKGUPN-BYYHNAKLSA-N CCCCC(CC)CN(C(C(C#N)=C1C)=O)C(O)=C1/N=N/c(cc1)cc(C#N)c1C#N Chemical compound CCCCC(CC)CN(C(C(C#N)=C1C)=O)C(O)=C1/N=N/c(cc1)cc(C#N)c1C#N OFEGXVATUKGUPN-BYYHNAKLSA-N 0.000 description 1
- YGTVWUPIFQQOHE-WCWDXBQESA-N CCCCN(C(C(C#N)=C1C)=O)C(O)=C1/N=N/c(cc1)cc(C#N)c1C#N Chemical compound CCCCN(C(C(C#N)=C1C)=O)C(O)=C1/N=N/c(cc1)cc(C#N)c1C#N YGTVWUPIFQQOHE-WCWDXBQESA-N 0.000 description 1
Classifications
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3665—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
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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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
(A) a colorant comprising a pigment and a dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator, and (E) a solvent, wherein the dye is a photosensitive resin composition comprising a lipophilic compound represented by the following formula (1), a photosensitive resin film produced using the photosensitive resin composition, and the photosensitive resin film Color filters.
[Chemical Formula 1]
(Wherein each substituent is as defined in the specification).
Description
The present invention relates to a photosensitive resin composition, a photosensitive resin film produced using the photosensitive resin composition, and a color filter comprising the photosensitive resin film.
Recently, as the spread of the large-screen liquid crystal display device has expanded, a demand for a new performance enhancement for the liquid crystal display device has been increasing. Among the components of the liquid crystal display device, the color filter is the most important color realizing device. Research is continuing.
In addition, in the case of a large-screen liquid crystal display device, the colorant concentration of the photosensitive resin composition is increased in manufacturing a color filter in order to increase the color purity. In order to increase productivity and yield in the production process, a photosensitive resin composition having a low developing speed and excellent sensitivity .
The color filter using the photosensitive resin composition can be produced by coating three or more kinds of hues on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like. Recently, a pigment dispersion method is widely used.
On the other hand, in a color filter made of a pigment type photosensitive resin composition, there is a limit of brightness and contrast ratio resulting from the pigment particle size. Further, in the case of a color imaging device for an image sensor, a smaller dispersion particle size is required for forming a fine pattern. In order to meet such a demand, attempts have been made to fabricate a photosensitive resin composition in which a dye that does not form particles is introduced instead of a pigment, thereby realizing a color filter having improved color characteristics such as brightness and contrast ratio. However, the dye-type photosensitive resin composition is difficult to commercialize due to its weak heat resistance, light resistance and chemical resistance.
Therefore, further research is needed to improve the photosensitive resin composition containing the pigment and the dye.
One embodiment is to provide a photosensitive resin composition having excellent brightness and coloring power.
Another embodiment is to provide a photosensitive resin film produced using the photosensitive resin composition.
Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.
One embodiment of the present invention relates to a colorant comprising (A) a pigment and a dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator and (E) a solvent, wherein the dye comprises a lipophilic compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 is a cyano group,
R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 aryl group,
n is an integer of 2 to 5 and m is an integer of 0 to 5, provided that 2? n + m? 5,
A is a substituted or unsubstituted C6 to C20 aromatic heterocycle or a substituted or unsubstituted C3 to C20 cycloaliphatic heterocycle.
The aromatic heterocycle and the alicyclic heterocycle may include at least one structure represented by the following formula (2) in the ring.
(2)
The aromatic heterocycle may be represented by the following formula (3).
(3)
In Formula 3,
R 3 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R 4 to R 6 are each independently a hydrogen atom, a cyano group, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
R 3 is a substituted or unsubstituted C 1 to C 20 alkyl group or a substituted or unsubstituted C 6 to C 20 aryl group, R 4 is a cyano group, R 5 is a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C6 to C20 aryl ring, R 6 may be a hydroxyl group.
The alicyclic heterocycle may be represented by the following formula (4).
[Chemical Formula 4]
In Formula 4,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
The oil-soluble compound represented by the formula (1) may be represented by any one of the compounds represented by the following formulas (5) to (9).
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
The fat-soluble compound may be a yellow dye.
The dye may be contained in an amount of 0.1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.
The pigment may comprise a green pigment, a red pigment or a combination thereof.
The pigment is a green pigment, and the colorant may be included in an amount of 2 to 22% by weight based on the total amount of the photosensitive resin composition.
Wherein the photosensitive resin composition comprises 2 to 22% by weight of the colorant (A) relative to the total amount of the photosensitive resin composition; 1 to 30% by weight of the binder resin (B); 1 to 15% by weight of the (C) photopolymerizable compound; 0.01 to 10% by weight of the photopolymerization initiator (D); And (E) the solvent balance.
The pigment is a red pigment, and the colorant may be contained in an amount of 1 to 19% by weight based on the total amount of the photosensitive resin composition.
Wherein the photosensitive resin composition comprises 1 to 19% by weight of the colorant (A) relative to the total amount of the photosensitive resin composition; 1 to 30% by weight of the binder resin (B); 1 to 15% by weight of the (C) photopolymerizable compound; 0.01 to 10% by weight of the photopolymerization initiator (D); And (E) the solvent balance.
The binder resin may be an acrylic binder resin.
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator, or a combination thereof.
Another embodiment provides a photosensitive resin film produced using the photosensitive resin composition.
Another embodiment provides a color filter comprising the photosensitive resin film.
The color filter may be a green color filter or a red color filter.
Other aspects of the present invention are included in the following detailed description.
The photosensitive resin composition according to one embodiment can provide a photosensitive resin film having excellent brightness and coloring power including a novel fat soluble compound and a color filter including the same.
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.
Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Cl, Br or I), a hydroxyl group, a nitro group, a cyano group, an amino group NH 2, NH (R 200), or N (R 201) (R 202), wherein R 200, R 201 and R 202 are the same or different, each independently being a C1 to C10 alkyl groups), amidino group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted heterocyclic group.
Unless otherwise specified in the specification, "alkyl group" means C1 to C20 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C20 cycloalkyl group, specifically C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and an " aryl group " means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.
(Meth) acrylate " refers to both " acrylic acid " and " methacrylic acid " It means both are possible.
As used herein, unless otherwise defined, " combination " means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.
Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.
Unless otherwise defined herein, " * " means the same or different atom or moiety connected to a formula.
Further, unless otherwise defined in this specification, the " maximum light absorbing region " means a region (range) showing the maximum absorbance.
One embodiment includes (A) a colorant comprising a pigment and a dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator, and (E) a solvent, wherein the dye comprises a lipophilic compound represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 is a cyano group,
R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkylene group, or a substituted or unsubstituted C6 to C20 aryl group,
n is an integer of 2 to 5 and m is an integer of 0 to 5, provided that 2? n + m? 5,
A is a substituted or unsubstituted C6 to C20 aromatic heterocycle or a substituted or unsubstituted C3 to C20 cycloaliphatic heterocycle.
In the case of the oil-soluble compound represented by the above formula (1), since the benzene ring necessarily contains at least two cyano groups, it can have excellent contrast ratio and brightness while maintaining the wavelength band similar to the conventional yellow dye. In addition, it has a similar or shorter wavelength band as compared with the conventional yellow pigment, such as yellow G, and has high heat resistance and coloring power, and is excellent in solubility in organic solvents such as cyclohexanone and PGMEA.
The fat-soluble compound represented by the above-mentioned formula (1) is a fat-soluble compound having an excellent solubility in an organic solvent, and its structure and use are different from those of a compound containing a water-soluble substituent (for example, a sulfonic acid group or the like) or a salt thereof.
The photosensitive resin composition according to one embodiment of the present invention makes it possible to manufacture a photosensitive resin film having excellent brightness and coloring power and a color filter including the same, by expressing the oil-soluble compound represented by the above formula (1) as a dye.
Each component will be described in detail below.
(A) Colorant
dyes
As described above, the dye includes the lipophilic compound represented by the above formula (1). For example, the dye may be a lipid-soluble compound represented by the formula (1).
For example, in Formula 1,
n is an integer of 2, and m may be an integer of 0.
For example, the aromatic heterocyclic ring and the alicyclic heterocyclic ring may contain at least one structure represented by the following formula (2) in the ring.
(2)
For example, the aromatic heterocyclic ring may be represented by the following formula (3).
(3)
In Formula 3,
R 3 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R 4 to R 6 are each independently a hydrogen atom, a cyano group, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
For example, the fat-soluble compound represented by Formula 1 may be represented by Formula 1-1 below.
[Formula 1-1]
In Formula 1-1,
R 1 to R 6 , n, and m are as described above.
For example, R 3 is a substituted or unsubstituted C 1 to C 20 alkyl group or a substituted or unsubstituted C 6 to C 20 aryl group, R 4 is a cyano group, and R 5 is a substituted or unsubstituted C 1 to C 20 alkyl group or A substituted or unsubstituted C6 to C20 aryl group, and R < 6 > may be a hydroxy group.
For example, the alicyclic heterocycle may be represented by the following formula (4).
[Chemical Formula 4]
In Formula 4,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
For example, the fat-soluble compound represented by Formula 1 may be represented by Formula 1-2.
[Formula 1-2]
In Formula 1-2,
R 1 , R 2 , R 7 , R 8 , n, and m are as described above.
The oil-soluble compound represented by the formula (1) contains an aromatic heterocyclic ring represented by the formula (3) or an alicyclic heterocyclic ring represented by the formula (4) in addition to at least two cyano groups, Absorbing region, and can have excellent heat resistance and coloring power.
For example, the oil-soluble compound represented by the formula (1) may be represented by one of the compounds represented by the following formulas (5) to (9).
[Chemical Formula 5]
[Chemical Formula 6]
(7)
[Chemical Formula 8]
[Chemical Formula 9]
The dye in the photosensitive resin composition according to one embodiment contains the compound represented by the above formula (1), for example, the formula (1-1) or the formula (1-2), so that a clear color can be expressed with a small amount of dye, It is possible to manufacture a display device having excellent coloring power as well as color characteristics such as contrast ratio. For example, the oil-soluble compound represented by Formula 1 may be a yellow dye, for example, a dye having a maximum light absorption region in a wavelength range of 150 nm to 450 nm, for example, 350 nm to 450 nm.
For example, the oil-soluble compound represented by Formula 1-1 (in Formula 1, A is an aromatic heterocycle and the aromatic heterocycle is a lipophilic compound represented by Formula 3) has a maximum absorption region in a wavelength range of 400 nm to 450 nm, Soluble lipophilic compound represented by Formula 1-2, wherein A is an alicyclic heterocycle and the alicyclic heterocycle is a lipophilic compound represented by Formula 4, is 150 nm to 400 nm, for example, And may have a maximum light absorption region in a wavelength range of 350 nm to 400 nm.
In general, dyes are the most expensive component of the components used in color filters. Therefore, in order to achieve a desired effect, for example, a high luminance and a high contrast ratio, it is necessary to use more expensive dye, so that the production cost has to be increased. However, when the oil-soluble compound represented by the above formula (1) is used as a dye in a color filter, such as a dye for dyeing, excellent color characteristics such as high luminance and high contrast ratio can be achieved even in a small amount, .
The dye may be contained in an amount of 0.1 wt% to 10 wt%, for example, 0.5 wt% to 8 wt% with respect to the total amount of the photosensitive resin composition. When the dye is included in the above range, the color reproducibility and the contrast ratio are excellent .
Pigment
The pigments may include, but are not limited to, yellow pigments, green pigments, red pigments, or combinations thereof. For example, the pigment may be included in the photosensitive resin composition in the form of a pigment dispersion.
The pigment dispersion may include a solid pigment, a solvent, and a dispersant for uniformly dispersing the pigment in the solvent.
The solid pigment may be present in the pigment dispersion in an amount ranging from 1% to 20%, such as 8% to 20%, such as 15% to 20%, such as 8% to 15% 20% by weight, such as 10% by weight to 15% by weight.
As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.
DISPERBYK-161, DISPERBYK-160, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, DISPERBYK- -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.
The dispersing agent may be contained in an amount of 1 to 20% by weight based on the total amount of the pigment dispersion. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition can be maintained because an appropriate viscosity can be maintained, so that optical, physical and chemical quality can be maintained when the product is applied.
As the solvent for forming the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether and the like can be used.
When the pigment is a green pigment, the green pigment and the colorant containing the dye may be contained in an amount of 2 to 22 wt% based on the total amount of the photosensitive resin composition. The dye represented by the above-mentioned formula (1) can be used as a yellow dye. If the content of the coloring agent including the green pigment and the above-mentioned (yellow) dye is within the above range, the luminance and coloring power will be excellent.
When the pigment is a red pigment, the colorant containing the red pigment and the dye may be contained in an amount of 1 wt% to 19 wt% based on the total amount of the photosensitive resin composition. The dye represented by the above-described formula (1) can be used as a yellow dye, and the content of the coloring agent including the red pigment and the above-mentioned (yellow) dye should be within the above range, so that the luminance and coloring power are excellent.
Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. Nickel complex pigments such as yellow pigment 150, and the like. However, the present invention is not limited thereto.
Examples of the green pigment include C.I. Green pigment 58, C.I. Green pigment 36, C.I. Green pigments 7, and the like, but the present invention is not limited thereto.
Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89, and the like, but the present invention is not limited thereto.
(B) binder resin
The binder resin may be an acrylic binder resin.
The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and may be a resin containing 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 included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic binder 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; (Meth) acrylamide, and the like. These may be used singly or in combination of two or more thereof.
Specific examples of the acrylic binder resin include polybenzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate (Meth) acrylic 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. Two or more kinds may be used in combination.
The weight average molecular weight of the binder resin may be from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 20,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the binder 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 in the production of a color filter.
The acid value of the binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 mgKOH / g. When the acid value of the binder resin is within the above range, the resolution of the pixel pattern is excellent.
The binder resin may be contained in an amount of 1% by weight to 30% by weight, for example, 1% by weight to 15% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, the color filter is excellent in developing property and the crosslinking property is improved, whereby excellent surface smoothness can be obtained.
(C) Photopolymerization compound
The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.
By having the ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.
Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.
Examples of commercially available products of photopolymerizable compounds are 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 -710 ® , 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 compound may be treated with an acid anhydride so as to give better developing properties.
The photopolymerizable compound may be contained in an amount of 1 wt% to 15 wt%, for example, 5 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above-mentioned range, the pattern forming process sufficiently cures upon exposure to light, which is excellent in reliability and developability in an alkaline developer.
(D) Light curing Initiator
The photopolymerization initiator is an initiator generally used in a photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, a oxime compound, Can be used.
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-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 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- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.
Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) Acetate and the like.
The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.
The photopolymerization initiator may be used together with a photosensitizer that generates a chemical reaction by transferring the energy after the light is absorbed and excited.
Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .
The photopolymerization initiator may be included in an amount of 0.01 wt% to 10 wt%, for example, 0.1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator is sufficiently cured upon exposure in the pattern formation step to obtain excellent reliability, and the pattern is excellent in heat resistance, light resistance, chemical resistance, resolution and adhesion, It is possible to prevent the transmittance from being lowered.
(E) Solvent
The solvent may be a material which has compatibility with the above-mentioned oil-soluble compound, pigment, binder resin, photopolymerizable compound and photopolymerization initiator but does not react. The solvent may be an organic solvent or a 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 monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.
Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be contained in an amount of 30% by weight to 90% by weight, such as 40% by weight to 85% 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 thus the processability in the production of the color filter is excellent.
(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 spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator, or a combination thereof.
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 BM-1000 ® of社, BM-1100 ®, and the like; Dainippon ingki Kagaku Kogyo (state) of the mechanical社pack F 142D ®, copper F 172 ®, the same F 173 ®, the same F 183 ®, Copper F 554 ®, etc .; Sumitomo M. (Note)社Pro rod FC-135 ®, the same FC-170C ®, copper FC-430 ®, the same FC-431 ®, and the like; Asahi Grass Co., Saffron S-112 ® of社, such S-113 ®, the same S-131 ®, the same S-141 ®, the same S-145 ®, and the like; Toray silicone (Note) ® SH-28PA of社, copper -190 ®, may be a commercially available product such as copper -193 ®, SZ-6032 ®, SF-8428 ®.
When the photosensitive resin composition according to one embodiment contains the fluorine-based surfactant in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition, coating uniformity is ensured, no unevenness occurs, (wetting) is excellent.
The photosensitive resin composition according to one embodiment may further include an epoxy compound to improve adhesion with the substrate.
Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.
The epoxy compound may be contained in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the above range, the adhesive property, heat resistance, and chemical resistance are excellent.
The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.
The content of the additive can be easily adjusted according to desired properties.
According to another embodiment, there is provided a photosensitive resin film produced using the photosensitive resin composition according to one embodiment.
The photosensitive resin film can be produced by a process of coating, exposing and developing the photosensitive resin composition on a substrate. Some of the processes may be omitted or added.
According to another embodiment, there is provided a color filter comprising the above-mentioned photosensitive resin film.
The color filter may be a green color filter or a red color filter, but is not limited thereto.
The pattern forming process in the color filter is as follows.
Applying the photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing or the like; Drying the applied photosensitive resin composition to form a photosensitive resin composition film; Exposing the photosensitive resin composition film; Developing the exposed photosensitive resin composition film with an aqueous alkali solution to produce a photosensitive resin film; And a step of heat-treating the photosensitive resin film. The process conditions and the like are well known in the art, and therefore, detailed description thereof will be omitted herein.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are only the preferred embodiments of the present invention, and the present invention is not limited to the following Examples.
(Synthesis of a fat-soluble compound)
Synthetic example 1: Synthesis of a lipid-soluble compound represented by the formula (5)
4-Aminophthalonitrile (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (2 mL of 1.25 M aqueous solution) to give an azonium ion. The pyridone compound (2.5 mmol) substituted with 2-ethylhexyl group NaOH aqueous solution to prepare an azo compound. At this time, the obtained solid was filtered, purified and vacuum-dried to obtain a fat-soluble compound represented by the following formula (5).
[Chemical Formula 5]
1 H NMR (300 MHz, CDCl 3 ) 7.88-7.85 (2H), 7.73-7.69 (1H), 3.87 (2H), 2.60 (3H), 1.79 (1H), 1.40-1.15 (8H), 0.93-0.88 6H).
GC / MS 416 m / z.
Synthetic example 2: Synthesis of the oil-soluble compound represented by the formula (6)
3-Aminophthalonitrile (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25M aqueous solution, 2 mL) to give an azonium ion. The pyridone compound (2.5 mmol) substituted with 2-ethylhexyl group NaOH aqueous solution to prepare an azo compound. At this time, the obtained solid was filtered, purified and vacuum-dried to obtain a fat-soluble compound represented by the following formula (6).
[Chemical Formula 6]
GC / MS 416 m / z.
Synthetic example 3: Synthesis of the oil-soluble compound represented by the formula (7)
4-Aminophthalonitrile (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25M aqueous solution, 2 mL) to prepare an azonium ion. The pyridone compound (2.5 mmol) substituted with n-butyl group was dissolved in an aqueous solution of NaOH In a weak basic aqueous solution to prepare an azo compound. At this time, the obtained solid was filtered, purified and vacuum-dried to obtain a fat-soluble compound represented by the following formula (7).
(7)
1 H NMR (300 MHz, CDCl 3 ) 7.88-7.85 (2H), 7.73-7.69 (1H), 3.86 (2H), 2.60 (3H), 1.50-1.12 (4H), 0.96-0.92 (3H).
Synthetic example 4: Synthesis of the oil-soluble compound represented by the formula (8)
4-Aminophthalonitrile (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25M aqueous solution, 2 mL) to make an azonium ion. This was added to a weakly basic aqueous solution of barbituric acid (2.5 mmol) Azo compound. The resulting solid was filtered, purified and vacuum-dried, and then 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) were added thereto. The reaction was carried out in a DMF solvent, followed by purification and vacuum drying to obtain a fat-
[Chemical Formula 8]
1 H NMR (300 MHz, CDCl 3 ) 14.3 (1H), 7.95-7.94 (1H), 7.86-7.80 (2H), 4.03-3.87 (4H), 1.78-1.62 (4H), 1.46-1.36 1.01-0.94 (6H).
Synthetic example 5: Synthesis of the oil-soluble compound represented by the formula (9)
4-Aminophthalonitrile (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25M aqueous solution, 2 mL) to make an azonium ion. This was added to a weakly basic aqueous solution of barbituric acid (2.5 mmol) Azo compound. The resulting solid was filtered, purified and vacuum-dried, and 4-iodotoluene (5.5 mmol) and potassium carbonate (7.5 mmol) were added thereto, followed by reaction in DMF solvent, purification, and vacuum drying to obtain a fat-
[Chemical Formula 9]
1 H NMR (300 MHz, CDCl 3 ) 14.3 (1H), 7.95-7.94 (1H), 7.86-7.80 (2H), 7.21 (2H), 7.06 (2H), 2.36
compare Synthetic example 1: To 10 Synthesis of displayed compounds
4-Aminophenol (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25 M aqueous solution, 2 mL) to make an azonium ion. This was added to a weakly basic aqueous solution of barbituric acid (2.5 mmol) Azo compound. The resulting solid was filtered, purified and vacuum-dried, and then 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) were added thereto, followed by reaction in DMF solvent, purification, and vacuum drying to obtain a fat-
[Chemical formula 10]
GC / MS 360 m / z.
compare Synthetic example 2: Synthesis of Compound Represented by Formula 11
Aniline (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25M aqueous solution, 2 mL) to give an azonium ion. The pyridone compound (2.5 mmol) substituted with a 2-ethylhexyl group was dissolved in an aqueous solution of NaOH In a weak basic aqueous solution to prepare an azo compound. At this time, the obtained solid was filtered, purified and vacuum-dried to obtain a fat-soluble compound represented by the following formula (11).
(11)
1 H NMR (300 MHz, CDCl 3 ) 7.53 (2H), 7.44 (2H), 7.36 (1H), 3.87 (2H), 2.60 (3H), 1.79 (6H).
compare Synthetic example 3: Synthesis of the compound represented by the formula (12)
Aniline (2.5 mmol) was added with hydrochloric acid (2.5 mL) and sodium nitrate (1.25 M aqueous solution, 2 mL) to make an azonium ion. The azo compound was added to a weakly basic aqueous solution in which barbituric acid (2.5 mmol) . The resulting solid was filtered, purified and vacuum-dried, and then 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) were added thereto, followed by reaction in DMF solvent, purification, and vacuum drying to obtain a fat-
[Chemical Formula 12]
1 H NMR (300 MHz, CDCl 3 ) 14.1 (1H), 7.71 (2H), 7.59 (2H), 7.46 (1H), 4.03-3.87 (4H), 1.78-1.62 , 1.01-0.94 (6H).
(evaluation)
Rating 1: Organic solvent Solubility in water
Diluted solvent (Anone) was added to 0.5 g of the compound synthesized in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3, and the solution was mixed with a mix rotor (MIXROTAR VMR-5) After stirring at 25 DEG C and 100 rpm for 1 hour, the solubility of each compound was determined. (Anone means cyclohexanone.)
Solubility evaluation criteria
2.5% by weight or more of the compound (solute) dissolved in the total amount of the diluting solvent: ○
Less than 2.5% by weight of compound (solute) dissolved in total diluent solvent Dissolution: X
It can be seen from Table 1 that the compounds of Synthesis Examples 1 to 5 which are the compounds according to one embodiment are superior to the compounds of Comparative Synthesis Examples 1 to 3 in solubility in an organic solvent, It can be confirmed that the color characteristics can be expressed.
Evaluation 2: Coloring power
The maximum absorption wavelength (? Max ) of the compounds synthesized in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 was measured with a UV-1800 UV-Vis spectrometer and is shown in Table 2 below. 20 mg of the compound synthesized in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 was dissolved in anion (cyclohexanone) to make 20 g of a concentrated solution. Then, 0.1 g of the concentrated solution was added again to 10 g to make a 0.001 wt% dilute solution. The spectroscopic measurement of the 0.001% by weight solution at room temperature was carried out, and the molar extinction coefficient was calculated from the following equation (1).
[Equation 1]
A = εcl
(A: maximum absorbance,?: Molar extinction coefficient, c: molar concentration, 1: optical path length)
It can be seen from Table 2 that unlike the compounds of Comparative Synthesis Examples 1 to 3, the compounds of Synthesis Examples 1 to 5, which are compounds according to one embodiment, contain a cyano group, It can be confirmed that it has better coloring power.
(Preparation of photosensitive resin composition)
Example 1 to Example 14, Reference example 1 to Reference example 4, Comparative Example 1 and Comparative Example 2
The photosensitive resin compositions according to Examples 1 to 14, Reference Examples 1 to 4, Comparative Examples 1 and 2 were prepared using the following components with the compositions shown in Tables 3 and 4 below.
Specifically, the content of the photopolymerization initiator was precisely measured, the solvent was then added, and the mixture was sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was sufficiently dissolved. To this, an acrylic binder resin and a photopolymerizable monomer were sequentially added, followed by stirring for about 1 hour. Subsequently, a pigment dispersion in which a solid pigment was dispersed and a dye were added, and other additives were added thereto, and finally the entire composition was stirred for 2 hours or more to prepare a photosensitive resin composition.
The specifications of each component used in the production of the photosensitive resin composition are as follows.
(A) Colorant
dyes
(A-1) The oil-soluble compound of Synthesis Example 1
(A-2) The oil-soluble compound of Synthesis Example 2
(A-3) The oil-soluble compound of Synthesis Example 3
(A-4) The oil-soluble compound of Synthesis Example 4
(A-5) The oil-soluble compound of Synthesis Example 5
Pigment
(A-6) Green pigment (ENF, G58)
(A-7) Red pigment (ENF, R254)
(A-8) Yellow pigment (ENF, Y138)
(A-9) Yellow Pigment (ENF, Y150)
(B) binder resin
Acrylic binder resin (SKY-095, Samsung SDI)
(C) Photopolymerization compound
The photopolymerizable compound (DPHA)
(D) Light curing Initiator
(D-1) oxime initiator (BASF, OXE-01)
(D-2) oxime initiator (BASF, OXE-02)
(E) Solvent
Propylene glycol monomethyl ether acetate (PGMEA)
(F) Other additives
Fluorine-based surfactant (DIC, F-554 (using 10% diluent))
Evaluation 3: Evaluation of color characteristics
The photosensitive resin compositions obtained in Examples 1 to 14, Reference Examples 1 to 4, and Comparative Example 1 and Comparative Example 2 were coated with a coating solution (Mikasa, Opticoat MS-A150) rpm and pre-baking was performed on a hot-plate at 90 ° C. Thereafter, the entire surface was exposed using an exposure machine (Ushio, HB-50110AA) under an exposure condition of 50 mj / cm 2 , and baking was performed at 230 캜 for 20 minutes in an oven condition to complete the preparation of the test piece. The color characteristics (luminance (Y), contrast ratio (CR)) were measured using an MCPD 3000 apparatus before and after the oven baking, and the results are shown in Table 5 below.
In the case of Examples 1 to 14, which are photosensitive resin compositions comprising a pigment and a coloring agent containing a lipid-soluble compound represented by Formula 1 as a dye, the photosensitive resin composition of Comparative Example 1 and Comparative Example 2 It can be confirmed that the coloring power, the luminance, and the contrast ratio are excellent.
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 (18)
(B) a binder resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator and
(E) a solvent,
Wherein the dye comprises a lipophilic compound represented by any one of the following formulas (1), (5), (6) and (7)
[Chemical Formula 1]
[Chemical Formula 5]
[Chemical Formula 6]
(7)
In Formula 1,
R 1 is a cyano group,
R 2 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a substituted or unsubstituted C6 to C20 aryl group,
n is an integer of 2 to 5 and m is an integer of 0 to 3, provided that 2? n + m? 5,
A is represented by the following formula (4)
[Chemical Formula 4]
In Formula 4,
R 7 and R 8 are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
Wherein the oil-soluble compound represented by the formula (1) is represented by the following formula (8) or (9).
[Chemical Formula 8]
[Chemical Formula 9]
Wherein the oil-soluble compound is a yellow dye.
Wherein the dye is contained in an amount of 0.1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.
Wherein the pigment comprises a green pigment, a red pigment or a combination thereof.
The pigment is a green pigment,
Wherein the colorant is contained in an amount of 2% by weight to 22% by weight based on the total amount of the photosensitive resin composition.
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
2% to 22% by weight of (A) the colorant;
1 to 30% by weight of the binder resin (B);
1 to 15% by weight of the (C) photopolymerizable compound;
0.01 to 10% by weight of the photopolymerization initiator (D); And
30% to 90% by weight of the solvent (E)
.
The pigment is a red pigment,
Wherein the colorant is contained in an amount of 1 to 19% by weight based on the total amount of the photosensitive resin composition.
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
1% to 19% by weight of (A) the colorant;
1 to 30% by weight of the binder resin (B);
1 to 15% by weight of the (C) photopolymerizable compound;
0.01 to 10% by weight of the photopolymerization initiator (D); And
30% to 90% by weight of the solvent (E)
.
Wherein the binder resin is an acrylic binder resin.
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; A fluorine-based surfactant, or a combination thereof.
Wherein the color filter is a green color filter or a red color filter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160008752A KR101895309B1 (en) | 2016-01-25 | 2016-01-25 | Photosensitive resin composition, photosensitive resin layer and color filter comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160008752A KR101895309B1 (en) | 2016-01-25 | 2016-01-25 | Photosensitive resin composition, photosensitive resin layer and color filter comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170088631A KR20170088631A (en) | 2017-08-02 |
| KR101895309B1 true KR101895309B1 (en) | 2018-09-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160008752A KR101895309B1 (en) | 2016-01-25 | 2016-01-25 | Photosensitive resin composition, photosensitive resin layer and color filter comprising the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101895309B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190056809A (en) * | 2017-11-17 | 2019-05-27 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102194976B1 (en) * | 2017-11-09 | 2020-12-24 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin using the same and color filter |
| KR102338286B1 (en) * | 2018-08-31 | 2021-12-09 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin using the same and color filter |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6044556A (en) * | 1983-08-22 | 1985-03-09 | Nippon Kayaku Co Ltd | Water-insoluble monoazo compound and dyeing using it |
| JPH05142863A (en) * | 1991-11-18 | 1993-06-11 | Ricoh Co Ltd | Electrophotographic toner |
| JP5799647B2 (en) * | 2010-09-22 | 2015-10-28 | 住友化学株式会社 | Compound |
| KR101690514B1 (en) * | 2012-12-28 | 2016-12-28 | 제일모직 주식회사 | Photosensitive resin composition for color filter and color filter using the same |
-
2016
- 2016-01-25 KR KR1020160008752A patent/KR101895309B1/en active IP Right Grant
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190056809A (en) * | 2017-11-17 | 2019-05-27 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
| KR102204707B1 (en) | 2017-11-17 | 2021-01-18 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170088631A (en) | 2017-08-02 |
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