KR20150005139A - Blue dye compounds, colored resin composition comprising the same for color filter and color filter using the same - Google Patents
Blue dye compounds, colored resin composition comprising the same for color filter and color filter using the same Download PDFInfo
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- KR20150005139A KR20150005139A KR1020130078508A KR20130078508A KR20150005139A KR 20150005139 A KR20150005139 A KR 20150005139A KR 1020130078508 A KR1020130078508 A KR 1020130078508A KR 20130078508 A KR20130078508 A KR 20130078508A KR 20150005139 A KR20150005139 A KR 20150005139A
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- LAPSFTOXWXPVTA-UHFFFAOYSA-N CCN(CC)c(cc1)ccc1/C(/c(cc1)c(C)cc1N(CC)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=C/C1=[N+](/CC)\CC[O]=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=O)=O Chemical compound CCN(CC)c(cc1)ccc1/C(/c(cc1)c(C)cc1N(CC)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=C/C1=[N+](/CC)\CC[O]=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=O)=O LAPSFTOXWXPVTA-UHFFFAOYSA-N 0.000 description 1
- SPIKGMWBIBVSRE-UHFFFAOYSA-N CCN(CC)c(cc1)ccc1/C(/c(cc1)c(C)cc1N(CC)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=CC1=[N+](CC)CC Chemical compound CCN(CC)c(cc1)ccc1/C(/c(cc1)c(C)cc1N(CC)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=CC1=[N+](CC)CC SPIKGMWBIBVSRE-UHFFFAOYSA-N 0.000 description 1
- ZCBQAHFXIRHJOZ-UHFFFAOYSA-N CCN(CC)c(cc1)ccc1/C(/c(cc1)ccc1N(CCOC(C(C)=C)=O)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=C/C1=[N+](/CC)\CC[O]=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=O)=O Chemical compound CCN(CC)c(cc1)ccc1/C(/c(cc1)ccc1N(CCOC(C(C)=C)=O)CCOC(C(C)=C)=O)=C(\C=C1)/C(OC)=C/C1=[N+](/CC)\CC[O]=S(C(F)(F)F)([N-]S(C(F)(F)F)(=O)=O)=O ZCBQAHFXIRHJOZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
-
- 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
-
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/032—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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Chemistry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
Description
More particularly, the present invention relates to a novel triarylmethane dye compound having improved solubility and high heat resistance as compared with conventional dyes, a blue resin composition for a color filter comprising the same, Color filter.
A liquid crystal display displays an image using the optical and electrical properties of a liquid crystal material. The liquid crystal display device has advantages such as light weight, low power, and low driving voltage as compared with a CRT, a plasma display panel and the like. A liquid crystal display device includes a liquid crystal layer disposed between glass substrates. Light generated from the light source passes through the liquid crystal layer, and the liquid crystal layer controls the transmittance of light. The light passing through the liquid crystal passes through the color filter layer, and a full color image is realized by adding color mixture using light passing through the color filter layer.
Dyeing methods, printing methods, electrodeposition methods and pigment dispersion methods are generally known as methods for producing color filters used in liquid crystal display devices, and methods using dyes have been studied from the past. However, when dyes are used, heat resistance, Chemical properties and the like are low compared with the pigment, so that it is not easy to apply. In addition, the pigment dispersion method is generally applied because dyeing method is not economical because of complicated process. Pigment has a lower transparency than dyes but has been overcome by advances in pigment refinement and dispersion techniques. The color filter fabricated by the pigment dispersion method is stable against light, heat, solvent, etc. since it uses pigment, and it is easy to fabricate a color filter for a large screen and a high-precision color display when patterning by a photolithography method is used, .
Pigments used in pigment-dispersed color resists include red, green and blue pigments, respectively, when forming an RGB color filter, and generally may further include yellow pigments, violet pigments, etc. to more effectively represent colors. In a method of producing a color filter by the pigment dispersion method, a color resist solution is first applied on a substrate with a spin coater and dried to form a coating film. Then, colored pixels are obtained by pattern exposure and development of a coated film, heat treatment is performed at a high temperature to obtain a first color pattern, and this operation is repeated according to the number of colors to produce a color filter. The most important factor that determines the performance of a color resist is the property of the pigment used as a colorant and its dispersibility and dispersed state. In recent years, along with the enlargement of the LCD and the high definition, the required characteristics of the color filter such as high transmittance of the colored layer, high contrast ratio, narrowing of the black matrix width and high reliability are increasing every year. Up to now, as a means for satisfying these requirements, the color characteristics such as brightness and contrast ratio have been satisfied by making the pigment as fine as possible.
However, in order to prepare a pigment dispersion, a pigment powder obtained by synthesis can not be used as it is in a stable dispersion state and for facilitating fineness, and a finishing process such as salt milling is required, and such a post- In addition, dispersants, pigment derivatives and many other additives are needed to stabilize the dispersed state, and it is possible to produce them only after a complicated and troublesome manufacturing process. And pigment dispersions require rigid storage and transport conditions to maintain optimal quality conditions.
In the case of the pigment dispersion, the pigment is present in the form of particles and not only the light is scattered but also the surface area of the pigment is rapidly increased due to the fineness of the pigment, and due to the uneven pigment particle generation due to the deterioration of the dispersion stability, There is a difficulty in.
In addition, various studies have recently been conducted to achieve high brightness, high contrast ratio and high resolution using pigments. However, due to problems such as pigment refinement and dispersion stability mentioned above, the properties of the color filter using a pigment as a colorant The improvement is insignificant.
As an alternative to this, studies have been made to improve the luminance and contrast ratio by using a hybrid type colorant which improves physical properties by mixing pigments and dyes, thereby improving a certain level of luminance and contrast ratio. However, , The effect of improving the physical properties is not so significant.
Recently, in order to solve such problems and achieve high brightness, high contrast ratio and high resolution, it has been studied to use dyes instead of pigments as colorants. Many attempts have been made with triarylmethane dyes as blue coloring agents. In general, the triarylmethane dye has a high transmittance at 420 to 450 nm of a color filter, and thus is a blue coloring agent for a color filter. However, the coloring agent for a color filter has a low solubility in a solvent used for a color filter, . Generally, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and the like are generally used as a solvent for use in a coloring composition for a color filter, , The solubility in cyclohexanone is easy to ensure, but the solubility in PGMEA or PGME is low. However, in the case of cyclohexanone, it is necessary to use a dye having high solubility for PGMEA or PGME as the use thereof as an environmentally harmful substance is prohibited.
Among the various studies on existing triarylmethane dyes, for example, mention is made of naphthalenesulfonic acid, a salt compound of an anion of naphthylamine sulfonic acid, a colored resin composition containing the same, and a color filter in a triarylmethane dye cation for improving solubility and heat resistance . However, these compounds have a low solubility in propylene glycol monomethyl ether acetate (PGMEA) and the like and have a problem of low heat resistance.
As another example, triarylmethane cations and anions of other dyes have been studied, but these compounds have some problems in that their solubility in an ester organic solvent such as PGMEA is lowered, although their heat resistance is partially improved.
Accordingly, an object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to solve the above-mentioned problems, and to solve the above problem, a triarylmethane dye having excellent color characteristics as a blue compound solves the problems of low solubility and heat resistance of PGMEA, To provide a dye compound.
The present invention also provides a blue resin composition for a color filter comprising the blue dye compound and a color filter using the blue resin composition.
In order to solve the above problems, the present invention provides a triarylmethane blue dye compound represented by the following formula (1).
[Chemical Formula 1]
In the above formula (1), X - is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion, R 1 And R 9 are the same or different and are each independently selected from among hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and a, b, and c are Independently, an integer of 0 to 4;
In addition, the R 1 To R < 6 & Each independently to R 10 may be represented by the [formula 1], wherein R 1 To R 6 Is at least one of R < 10 >
[Structural formula 1]
In the above structural formula 1, n is an integer of 1 to 20, and R < 11 > is hydrogen or methyl.
According to one embodiment of the present invention, R 1 may be connected to R 2 , R 3 to R 4 , and R 5 to R 6 to form a saturated or unsaturated ring.
According to an embodiment of the present invention, each of R 7 , R 8 and R 9 is independently a substituted or unsubstituted C 1 -C 20 alkoxy group or halogen.
In order to solve the above problems, the present invention also provides a colorant composition comprising a blue dye compound, a binder resin, a reactive unsaturated compound, a polymerization initiator, an organic solvent and an additive, wherein the blue dye compound is triarylmethane A blue dye compound for a color filter.
The blue dye compound of the present invention may further include at least one selected from the group consisting of xanthene dyes, cyanine dyes, and azapopyrine dyes together with the triarylmethane blue dye compound represented by the formula (1).
The blue dye compound of the present invention may be 0.01% by weight to 50% by weight based on the total weight of the blue resin composition.
The blue resin composition for a color filter according to the present invention may further comprise a blue pigment, if necessary, and the blue pigment may be a copper phthalocyanine blue pigment.
The binder resin according to the present invention is not particularly limited as long as it is a resin capable of exhibiting binding force, and may be a known film-forming resin.
The reactive unsaturated compound of the present invention may be selected from the group consisting of thermosetting monomers and oligomers, photocurable monomers and oligomers, and combinations thereof.
The polymerization initiator of the present invention may be selected from the group consisting of a thermal curing initiator, a photo-curing initiator, and a combination thereof.
Further, a color filter comprising the blue resin composition for a color filter is provided.
The triarylmethane blue dye compound according to the present invention has excellent solubility and high heat resistance to propylene glycol monomethyl ether acetate (PGMEA). Accordingly, when the triarylmethane blue dye compound according to the present invention is used, it is possible to manufacture a color filter having a higher luminance and a higher contrast ratio than a color filter using a conventional pigment.
Hereinafter, the present invention will be described in more detail.
Recently, dyes having higher luminance than pigments have been developed as coloring agents for color filters. However, dyes generally have much lower heat resistance than pigments, and their solubility in organic solvents used in color filters is generally low. Therefore, in order to be used as a coloring agent for a color filter, high solubility in an organic solvent is required, high heat resistance and high brightness must be satisfied at the same time, but dyes satisfying these requirements are rare.
The blue dye compound according to the present invention is a blue coloring agent for a color filter which is improved in solubility and heat resistance characteristics of triarylmethane excellent in color characteristics and is characterized by being suitable for use in a blue composition of a color filter.
The blue dye compound according to the present invention is characterized by being a triarylmethane compound represented by the following formula (1).
[Chemical Formula 1]
In the above formula (1), X - is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion, R 1 And R 9 are the same or different and are each independently selected from among hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms, and a, b, and c are Independently, an integer of 0 to 4;
The R 1 To R < 6 & Each independently to R 10 may be represented by the [formula 1], wherein R 1 To R 6 Is at least one of R < 10 >
[Structural formula 1]
In the above structural formula 1, n is an integer of 1 to 20, and R < 11 > is hydrogen or methyl.
According to one embodiment of the present invention, R 1 may be connected with R 2 , R 3 with R 4 , and R 5 with R 6 to form a saturated or unsaturated ring.
According to an embodiment of the present invention, each of R 7 , R 8 and R 9 is independently a substituted or unsubstituted C 1 -C 20 alkoxy group or halogen.
The blue resin composition for a color filter according to the present invention includes the above blue dye compound, a binder resin, a reactive unsaturated compound, a polymerization initiator, an organic solvent and an additive, and may further comprise a blue pigment, if necessary.
The blue dye compound may further comprise one or more kinds of other dyes in combination with the triarylmethane compound represented by the general formula (1), and the additional dyes generally include xanthene Dyes, cyanine dyes, azapphyrin dyes, and the like.
The blue dye compound optionally containing one or more other dyes together with the compound according to the formula 1 may be contained in an amount of 0.01% to 50% by weight based on the total weight of the blue resin composition. When the blue dye compound is included in the above range Excellent solubility in solvents and excellent heat resistance.
The blue pigment may be selected from one or more of blue pigments commonly used in conventional colored resin compositions for color filters, and may include a copper phthalocyanine-based blue pigment. Examples of the copper phthalocyanine-based blue pigment include compounds classified in pigment index (published by The Society of Dyers and Colourists) as pigments. Specific examples include C.I. 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, and the like.
The binder resin is not particularly limited as long as it is a resin capable of exhibiting binding force, and particularly known film forming resins are useful.
For example, cellulose resins such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, acrylic acid resin, alkyd resin, melamine resin, epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyamide, polyamide- A binder such as polyimide and the like are useful.
In addition, the binder includes a resin having a photopolymerizable unsaturated bond, and may be, for example, an acrylic acid resin. In particular, homopolymers and copolymers of polymerizable monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, styrene and styrene derivatives, methacrylic acid, itaconic acid, maleic acid, Copolymers between polymerizable monomers, such as anhydrides, monoalkyl maleates, including caryobut groups, and polymeric monomers, such as methacrylic acid, styrene and styrene derivatives, are useful.
Examples thereof include compounds each containing an oxirane ring and an ethylenically unsaturated compound, such as glycidyl methacrylate, acryloylglycidyl ether, monoalkylglycidyl itaconate, etc., and carboxyl-containing polymerization A reaction product of a compound and a compound each containing a hydroxyl group and an ethylenically unsaturated compound (unsaturated alcohol) (e.g., allyl alcohol, 2-buten-4-ol, oleyl alcohol, 2-hydroxyethylmethacryl Acrylamide, etc.) and a carboxyl-containing polymer compound, and such a binder may contain an unsaturated compound having no isocyanate group.
The equivalent of the unsaturation of the binder (molecular weight of the binder per unsaturated compound) may generally range from 200 to 3,000, in particular from 230 to 1,000, in order to provide adequate photopolymerization as well as film hardness. In order to provide sufficient alkali developability after film exposure, the acid number may generally be from 20 to 300, in particular from 40 to 200. The average molecular weight of the binder is preferably 1,500 to 200,000, especially 10,000 to 50,000 g / mol.
The reactive unsaturated compound may be selected from the group consisting of a thermosetting monomer or an oligomer, a photo-curable monomer or oligomer, and a combination thereof. Preferably, the reactive unsaturated compound may be the photo-curable monomer. The reactive unsaturated compound may have one or more reactive double bond Group.
Useful photocurable monomers in this context are, in particular, reactive solvents or reactive diluents, for example mono-, di-, tri- and multifunctional acrylates and methacrylates, vinyl ethers, glycidyl ethers and the like. Additional reactive groups include aryl, hydroxyl, phosphate, urethane, secondary amines, N-alkoxymethyl groups and the like.
Monomers of this type are known in the art and are described, for example, in Roempp, Lexikon, Lacke und Druckfarben, et al. Ulrich Zorll, Thimem Verlag Stuttgart-New York, 1998, p 491/492. The choice of monomers will depend, inter alia, on the type and intensity of the irradiation used, the desired reaction by the photoinitiator and the film properties. These photocurable monomers may be used alone or in combination of monomers.
The polymerization initiator may be a thermosetting initiator, a photo-curing initiator, or a combination thereof, and may preferably be a photo-curing initiator. Such a photo-curing initiator may be, for example, the result of absorption of visible light or ultraviolet light, To form a reaction intermediate capable of inducing polymerization of the binder. Photoinitiators or are known in the art, see for example Roempp, Lexikon, Lacke und Druckfarben, et al. Ulrich Zorll, Thimem Verlag Stuttgart-New York, 1998, p 445/446.
Such organic solvents are, for example, ketones, alkylene glycol ethers, alcohols and aromatic compounds. Examples of the ketone group include acetone, methyl ethyl ketone, cyclohexanone, and the alkylene glycol ether group includes methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methyl solosorbate acetate , Ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether Triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol t-butyl ether acetate, triethylene glycol methyl ether acetate, , Triethylene glycol butyl ether acetate and triethylene glycol t-butyl ether acetate. The alcohol group includes methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like , And aromatic solvents include benzene, toluene, xylene, N-methyl-2-pyrrolidone and ethyl N-hydroxymethylpyrrolidone-2 acetate. Additional solvents include 1,2-propanediol diacetate, 3-methyl-3-methyl-3-methoxybutyl acetate, ethyl acetate, tetrahydrofuran and the like. These solvents may be used alone or as a mixture.
Such additional additives may be used without limitation as long as they meet the respective purposes. As a preferable example, fatty acids, fatty amines, alcohols, bean oil, wax, rosin, resins, benzotriazole derivatives and the like can be used for improving the surface texture. More preferably, stearic acid or behenic acid may be used as the fatty acid, and stearylamine may be used as the fatty amine.
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. 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 invention as defined by the appended claims. It will be clear to those who have knowledge.
<Examples>
1. Synthesis of intermediate compounds
(1) Synthesis of Compound of Formula (I)
A compound of the formula (I) was synthesized according to the following Reaction Scheme 1.
[Reaction Scheme 1]
(I)
0.498 mol of 4- (N, N-diethylamino) -benzoic acid and 200 g of toluene were added and stirred. Thereafter, 0.800 mol of thionyl chloride was added dropwise, and then the temperature was raised to 80 DEG C and reacted for 1 hour. After the reaction, the thionyl chloride and toluene were removed by distillation under reduced pressure to obtain 4- (N, N-diethylamino) -benzoyl chloride.
After 0.620 mmol of anhydrous aluminum chloride and 240 g of dichloroethane were stirred, cooled, and the temperature of the solution was kept below 5 ° C, the previously obtained 4- (N, N-diethylamino) -benzoyl chloride was dissolved in 120 g of dichloroethane, Lt; / RTI > 0.498 mol of 4- (N, N-diethylamino) -methtylidine was added dropwise to the reaction solution, and after the reaction solution was allowed to reach room temperature, the reaction was terminated by adding ice water. Sodium hydroxide solution was added thereto to adjust the pH to 11 or higher, followed by filtering with diatomaceous earth to remove insolubles and layer separation. The resulting organic layer was concentrated under reduced pressure. The compound obtained by concentration under reduced pressure was subjected to column chromatography to recover 0.152 mol of the compound of the formula (I).
(2) Synthesis of Compound of Formula (II)
[Formula II] was synthesized according to the following Reaction Scheme 2.
[Reaction Scheme 2]
[Formula II]
The synthesis was carried out in the same manner as in the synthesis of the compound of the formula [I] except that 4- (N, N-diethylamino) -methachloroaniline was used instead of 4- (N, N-diethylamino) 0.136 mol of the compound of the formula (II).
(3) Synthesis of Compound (III)
[Formula III] was synthesized according to the following Reaction Scheme 3.
[Reaction Scheme 3]
[Formula (III)
Synthesis was carried out in the same manner as in the synthesis of the compound of the formula (I) except that 4- (N, N-diethylamino) -methanisidine was used instead of 4- (N, To obtain 0.106 mol of the compound of the formula (III).
(4) Synthesis of compound of formula (IV)
The compound of the formula (IV) was synthesized according to the following scheme (4).
[Reaction Scheme 4]
[Formula IV]
0.300 mol of N-ethyl, N-hydroxyethylaniline and 0.330 mol of triethylamine were dissolved in 200 mL of dichloromethane and dissolved by stirring. Then, 0.330 mol of methacrylic anhydride was added, and the temperature was raised to 40 캜 and maintained. After completion of the reaction, water was added and the layers were separated, and 50 mL of a saturated sodium chloride solution was further added, followed by stirring for 30 minutes. After the layer separation, the organic layer was dried under reduced pressure and purified to obtain 0.282 mol of the formula IV.
(5) Synthesis of compound of formula (V)
A compound of the formula (V) was synthesized according to the following Reaction Scheme 5.
[Reaction Scheme 5]
[Formula V]
Synthesis was carried out in the same manner as in the synthesis of the compound of the formula (IV). Except that N-ethyl, N-hydroxyethylmethltoluidine was used instead of N-ethyl, N-hydroxyethylaniline to obtain 0.273 mol of a compound of the formula (V).
(6) Synthesis of Compound of Formula (VI)
[Formula VI] was synthesized according to the following Reaction Scheme 6.
[Reaction Scheme 6]
(VI)
0.300 mol of N, N-dihydroxyethylaniline and 0.660 mol of triethylamine were added 300 mL of dichloromethane and dissolved by stirring. Then, 0.660 mol of methacrylic anhydride was added, and the temperature was raised to 40 캜 and maintained. After completion of the reaction, water was added and the layers were separated, and 50 mL of a saturated sodium chloride solution was further added, followed by stirring for 30 minutes. After the layer separation, the organic layer was dried under reduced pressure and purified to obtain 0.280 mol of the compound of the formula (VI).
(7) Synthesis of compound of formula (VII)
The compound of the formula (VII) was synthesized according to the following scheme (7).
[Reaction Scheme 7]
[Formula VII]
Synthesis was carried out in the same manner as in the synthesis of the compound of the formula (VI). However, N, N-dihydroxyethylmethtolide was used instead of N, N-dihydroxyethylaniline to obtain 0.275 mol of the compound of the formula (VII).
(8) Synthesis of compound of the formula (VIII)
[Chemical Formula (VIII)] was synthesized according to the following Reaction Scheme 8.
[Reaction Scheme 8]
[Formula I] [Formula IV] [Formula VIII]
0.100 mol of the compound of Formula (I) and 140 g of toluene were added and stirred. Then, 0.150 mol of phosphorus oxychloride was added and stirred for 15 minutes. 0.003 mol of 4-methoxyphenol and 0.030 mol of [Formula IV] were added, and the mixture was heated to reflux for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and water was added thereto, followed by stirring. After layer separation, concentration under reduced pressure was carried out, and the obtained compound was purified to obtain 0.026 mol of a compound of the formula (VIII).
(9) Synthesis of Compounds (IX to IX)
Compounds of formulas (IX) to (IX) were synthesized in the same manner as in the synthesis of compound of formula (VIII) by selecting benzophenone and aniline derivatives as shown in Table 1 below.
[Formula IX] [Formula X] [Formula XI]
[Formula XII] [Formula XIII] [Formula XIV]
(XVI) < RTI ID = 0.0 > (XVI) <
[Formula XVIII] [Formula XIX]
2. According to the present invention Triarylmethane Synthesis of blue dye compounds
(One) Synthetic example 1: Synthesis of Compound (2)
A compound of Formula 2 was synthesized according to Reaction Scheme 9 below.
[Reaction Scheme 9]
[Formula (VIII) < EMI ID =
0.010 mol of the compound of the formula (VIII) was dissolved in 50 g of MeOH, and then 0.011 mol of lithium bistrifluoromethanesulfonimide was added thereto as a 20% aqueous solution to replace the salt. After filtration, the resulting compound was dissolved in chloroform, washed with water, and concentrated under reduced pressure to obtain 0.007 mol of a compound of formula (2).
(2) Synthetic example 2 to 24: Synthesis of compounds of formulas (3) to (25)
(VIII) to (XIX) were substituted with lithium bistrifluoromethanesulfonimide (A) and sodium trifluoromethanesulfonate (B) in the same manner as in Synthesis Example 1 .
[Chemical Formula 2] < EMI ID =
[Chemical Formula 5] < EMI ID =
[Chemical Formula 8]
[Chemical Formula 12] [Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 18] [Chemical Formula 19]
[Chemical Formula 20]
[Chemical Formula 23] [Chemical Formula 25]
3. Comparative Example 1: Synthesis of Compound
[Chemical Formula VIII]
0.010 mol of the compound of formula (VIII) was dissolved in methanol (50 mL), and then 0.011 mol of sodium p-toluenesulfonate was added thereto in 20% aqueous solution to replace the salt. After filtration, the resulting compound was dissolved in chloroform, washed with water, and concentrated under reduced pressure to obtain 0.004 mol of a compound of the formula (26).
4. Experimental Example 1: Solubility evaluation
Synthesis Examples 1 to 6 and Comparative Example 1 and Comparative Example 2 (Formula (VIII)) Dye compounds were dissolved in PGMEA to confirm their respective solubilities, and the results are shown in Table 3 below.
As shown in the above Table 3, it can be confirmed that the blue dye compounds of Formulas 2 to 25 of Synthesis Examples 1 to 24 according to the present invention have a high solubility of 5% or more in PGMEA, In the case of the non-substituted Comparative Example 2, the solubility of PGMEA < 1% is considerably low. In addition, in Comparative Example 1 in which Comparative Example 2 was replaced with sodium para-toluenesulfonate, the solubility was improved as compared with Comparative Example 2, but it was considerably lower than that of the compound according to the present invention. As described above, it can be confirmed that the blue dye compound according to the present invention has excellent solubility in an organic solvent such as PGMEA.
5. Preparation of blue resin composition for color filter and measurement of heat resistance
(One) Example 1. Preparation of blue resin composition for color filter
A photosensitive blue resin composition was prepared in the following composition.
(a) Binder resin: 2.7 g of a copolymer (Mw = 20000) of benzylmethacrylate / methacrylic acid (60: 40 mass ratio)
(b) Acrylic monomer: 10 g of dipentaerythritol hexaacrylate
(c) Blue dye compound: Synthesis Example 1 2.3 g
(d) Photopolymerization initiator: 2 g of Irgaeure OXE-01 manufactured by BASF
(e) Solvent: Propylene glycol monomethyl ether acetate 83 g
(2) Example 2 to Example 24. Preparation of blue resin composition for color filter
A photosensitive blue resin composition was prepared in the same manner as in Example 1 except that a blue dye compound was prepared using 2.3 g of the compound according to Synthesis Examples 2 to 24 above.
6. Comparative Example 3. Preparation of blue resin composition for color filter
A photosensitive blue resin composition was prepared in the same manner as in Example 1 except that 2.3 g of the compound of Comparative Example 1 was used instead of Synthesis Example 1.
7. Comparative Example 4. Preparation of blue resin composition for color filter
A photosensitive blue resin composition was prepared in the same manner as in Example 1 except that 2.3 g of a compound of the formula was used instead of the compound of Synthesis Example 1.
8. Experimental Example 2. Heat resistance measurement
For measurement of heat resistance, the blue resin compositions for color filters prepared in the above Examples and Comparative Examples were respectively spin-coated on a glass substrate having a size of 10 cm × 10 cm to a thickness of 2 μm and prebaked (pre -bake), followed by cooling at room temperature for 1 minute. This was exposed using an exposure machine at an exposure amount of 100 mJ / cm 2 (based on 365 nm).
After post-baking for 30 minutes in a convection oven at 220 ° C, the color characteristics were confirmed using a spectrophotometer, MCPD 3700, manufactured by Otsuka electronic Co., Ltd., and an additional one hour at 220 ° C in a convection oven After the heat treatment was performed, the color characteristic was confirmed again, and the value of [Delta] Eab * was determined and shown in Table 4 below.
Generally, it is known that satisfies the reliability because it satisfies ΔEab * 3 or less.
It can be seen that the reliability is satisfied at DELTA Eab * 3 or less in Examples 1 to 24. In the case of Comparative Example 1 and Comparative Example 2, it is understood that the heat resistance is greatly deteriorated. Therefore, the blue resin composition for a color filter according to the present invention shows excellent heat resistance.
Claims (11)
[Chemical Formula 1]
In the above formula (1)
X < - > is trifluoromethanesulfonic acid or bistrifluoromethanesulfonimide anion,
R 1 To R < 9 > are the same or different from each other and each independently selected from hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aromatic hydrocarbon having 6 to 10 carbon atoms,
a, b and c are each independently an integer of 0 to 4,
The R 1 To R 9 , R < 1 & To R < 6 & Each independently to R 10 may be represented by the [formula 1], wherein R 1 To R 6 Is at least one of R < 10 > represented by [formula 1]
[Structural formula 1]
In the above structural formula 1, n is an integer of 1 to 20, and R < 11 > is hydrogen or methyl.
And R 7 , R 8 and R 9 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or a halogen.
Wherein R 1 is R 2 , R 3 is R 4 , and R 5 is each connected to R 6 to form a saturated or unsaturated ring.
The triarylmethane blue dye compound according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (2) or (25)
[Chemical Formula 2] < EMI ID =
[Chemical Formula 5] < EMI ID =
[Chemical Formula 8]
[Chemical Formula 12] [Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 18] [Chemical Formula 19]
[Chemical Formula 20]
[Chemical Formula 23] [Chemical Formula 25]
Wherein the blue dye compound is a blue dye compound represented by the formula (1) according to claim 1.
Wherein the blue dye compound further comprises at least one selected from xanthene dyes, cyanine dyes, and azapopyrine dyes.
Wherein the blue dye compound is 0.01% by weight to 50% by weight based on the total weight of the blue resin composition.
Wherein the blue resin composition may further comprise a blue pigment, and the blue pigment is a copper phthalocyanine blue pigment.
The reactive unsaturated compound may be a thermosetting monomer or oligomer; Photocurable monomers or oligomers; And a combination thereof. ≪ / RTI >
Wherein the polymerization initiator is selected from the group consisting of a thermal polymerization initiator, a photopolymerization initiator, and a combination thereof.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130078508A KR20150005139A (en) | 2013-07-04 | 2013-07-04 | Blue dye compounds, colored resin composition comprising the same for color filter and color filter using the same |
| PCT/KR2014/004888 WO2015002381A1 (en) | 2013-07-04 | 2014-06-02 | Blue dye compound, blue resin composition for color filter comprising same and color filter using same |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020130078508A KR20150005139A (en) | 2013-07-04 | 2013-07-04 | Blue dye compounds, colored resin composition comprising the same for color filter and color filter using the same |
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| KR20150005139A true KR20150005139A (en) | 2015-01-14 |
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| WO (1) | WO2015002381A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9753368B2 (en) | 2015-10-14 | 2017-09-05 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, photosensitive resin film using the same and color filter |
| CN107168011A (en) * | 2016-03-07 | 2017-09-15 | 东友精细化工有限公司 | Cyan photosensitive polymer combination, cyan filter and display device comprising it |
| KR20180020031A (en) | 2016-08-17 | 2018-02-27 | 한국화학연구원 | Dimer-type triarylmethane dye compounds, blue resin composition comprising the same for color filter and color filter using the same |
| KR20200109795A (en) * | 2019-03-14 | 2020-09-23 | 동우 화인켐 주식회사 | Light scattering resin composition, scattering layer and image display device using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220076149A (en) | 2020-11-30 | 2022-06-08 | 이리도스 주식회사 | A blue colored composition for coms image sensor comprising xanthene compound, cross-linking acrylic monomer, acrylic monomer having phosphoric acid group and solvent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5772263B2 (en) * | 2010-07-30 | 2015-09-02 | Jsr株式会社 | Coloring composition, color filter and display element |
| CN102408753A (en) * | 2010-09-15 | 2012-04-11 | Jsr株式会社 | Alkaline colorant, colored composition, color filter and display element |
| KR101175198B1 (en) * | 2010-09-24 | 2012-08-20 | 디아이씨 가부시끼가이샤 | Compound and color filter |
| TWI546574B (en) * | 2011-06-01 | 2016-08-21 | Jsr股份有限公司 | Coloring composition, color filter and display element |
| KR101400185B1 (en) * | 2011-11-29 | 2014-06-19 | 제일모직 주식회사 | Photosensitive resin composition for color filter and color filter prepared using the same |
-
2013
- 2013-07-04 KR KR1020130078508A patent/KR20150005139A/en not_active Application Discontinuation
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- 2014-06-02 WO PCT/KR2014/004888 patent/WO2015002381A1/en active Application Filing
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9753368B2 (en) | 2015-10-14 | 2017-09-05 | Samsung Sdi Co., Ltd. | Photosensitive resin composition, photosensitive resin film using the same and color filter |
| CN107168011A (en) * | 2016-03-07 | 2017-09-15 | 东友精细化工有限公司 | Cyan photosensitive polymer combination, cyan filter and display device comprising it |
| CN107168011B (en) * | 2016-03-07 | 2021-04-13 | 东友精细化工有限公司 | Cyan photosensitive resin composition, cyan color filter comprising same, and display device |
| KR20180020031A (en) | 2016-08-17 | 2018-02-27 | 한국화학연구원 | Dimer-type triarylmethane dye compounds, blue resin composition comprising the same for color filter and color filter using the same |
| KR20200109795A (en) * | 2019-03-14 | 2020-09-23 | 동우 화인켐 주식회사 | Light scattering resin composition, scattering layer and image display device using the same |
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| WO2015002381A1 (en) | 2015-01-08 |
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