KR20160112479A - Self emission type photosensitive resin composition, color conversion layer color filter and image display device using the same - Google Patents
Self emission type photosensitive resin composition, color conversion layer color filter and image display device using the same Download PDFInfo
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- KR20160112479A KR20160112479A KR1020150038271A KR20150038271A KR20160112479A KR 20160112479 A KR20160112479 A KR 20160112479A KR 1020150038271 A KR1020150038271 A KR 1020150038271A KR 20150038271 A KR20150038271 A KR 20150038271A KR 20160112479 A KR20160112479 A KR 20160112479A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—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
Abstract
The self-luminescent photosensitive resin composition according to the present invention comprises an alkali-soluble resin, a fluorescent dye, a photopolymerization initiator, a photopolymerizable compound and a solvent, wherein the alkali-soluble resin has the following formula 1 and has a glass transition temperature of less than 0 ° C do.
[Chemical Formula 1]
(Wherein R 1 is hydrogen, a C 1 to C 12 aliphatic hydrocarbon, or a C 1 to C 12 aromatic hydrocarbon).
Description
The present invention relates to a self-luminescent photosensitive resin composition, a color conversion layer color filter manufactured using the same, and an image display device.
Recently, the display industry has undergone drastic changes from CRT (cathode-ray tube) to flat panel displays such as PDP (plasma display panel), OLED (organic light-emitting diode) and LCD (liquid-crystal display). Among them, LCD is widely used as an image display device used in almost all industries, and its application range is continuously expanding.
The LCD achieves full color by mixing the three primary colors that transmit white light generated from the backlight unit through the liquid crystal cell while controlling the transmittance and passing through the red, green, and blue color filters.
CCFL (Cold Cathode Fluorescent Lamp) is used as the light source of the backlight unit. In this case, since the backlight unit must be always supplied with power to the CCFL, power consumption is consumed. Also, it is pointed out that the color recall rate of about 70% compared with the existing CRT and the environmental pollution problems due to the addition of mercury are disadvantageous.
As a substitute product for solving the above problem, researches on a backlight unit using a light emitting diode (LED) have been actively conducted. When LEDs are used as a backlight unit, they exceed 100% of the NTSC (National Television System Committee) color reproduction range specification, and can provide a more vivid image quality to consumers.
In order to improve the efficiency of the backlight light source, the same industry has proposed a method by changing the material and structure of the color filter and the LCD panel.
The color filter forms a pixel of each color through a patterning process after applying a dispersion composition containing a pigment or a dye. Such a pigment and a dye cause a problem of lowering the transmission efficiency of the backlight light source. The lowering of the transmission efficiency results in lowering the color reproducibility of the display device, which makes it difficult to realize a high-quality screen.
The problem of low color reproducibility can be solved by increasing the light efficiency of the color filter, and a method of introducing the color conversion layer (or the light conversion layer) by increasing the thickness of the color filter or stacking or adjacent thereto is proposed .
1 is a schematic diagram showing the role of a color conversion layer in an image display device. As shown in Fig. 1, a light source generated from a
Conventionally, dyes and pigments are used as the composition of the color conversion layer. However, it is difficult to expect the light efficiency improvement only with such dyes and pigments, and the luminance is lowered. Thus, the use of a fluorescent material as a material of the color conversion layer 3 has been proposed.
The fluorescent material is excited by the blue light emitted from the
Korean Patent Laid-Open Publication No. 2004-0048218 discloses a color conversion layer having a fluorescent material. The Korean patent publication No. 2012-0048218 discloses a color conversion layer having a fluorescent material, which is disposed between a backlight unit and a substrate or disposed on an upper portion of a shutter, And a light-converting portion having at least one fluorescent substance for converting the light into the light of the light source.
Korean Patent Laid-Open Publication No. 2013-0083807 proposes a liquid crystal display device having a backlight unit capable of improving light efficiency. In order to improve light efficiency, a fluorescent material, a quantum dot, a white scattering material, an electroluminescence ) Materials and photoluminescence materials as well as a variety of other materials.
Japanese Laid-Open Patent Application No. 2013-077825 discloses a method of introducing a color conversion layer made of a green light emitting phosphor to form the brightness of a white light emitting diode (LED).
These patents have attempted to improve the quality of a display device by introducing a color conversion layer including a phosphor or the like. In this case, the method of forming the color conversion layer is not directly referred to, or even if it is mentioned, And the like.
The color conversion layer may be formed in a pattern corresponding to the red (R) and green (G) pixel portions of the color filter, respectively, as shown in Fig. 1, wherein a phosphor of several hundred microns in size for the color conversion layer is dissolved And thus it is difficult to realize a fine pattern and it is not easy to control physical properties such as thickness.
This difficulty can be solved as the micropattern can be realized through the photolithography method using the photosensitive resin composition.
In the case of a conventional photosensitive resin composition, a photoinitiator is essentially used for polymerization. In addition to lowering the fluorescence efficiency of the phosphor due to the radicals generated in the photoinitiator, in a post-baking process performed during the photolithography process, The layer has become yellowed and brought new problems.
Korean Unexamined Patent Publication No. 2007-0133687 discloses an antioxidant capable of preventing the oxidation of the photosensitive resin composition during the production of the photosensitive resin composition to improve the thermal stability and is used in combination with an acrylic binder resin and an acrylic carboxylate resin Which is capable of improving the thermal properties by increasing the crosslinking formation by the photoinitiation reaction. However, in this case, the heat resistance is still insufficient.
SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a self-luminescent photosensitive resin composition which improves the fluorescence efficiency and processability by using an alkali-soluble resin having a specific structure in the color conversion layer and provides a color conversion layer with high sensitivity and high efficiency The purpose is to provide.
In order to achieve the above object, the self-luminescent photosensitive resin composition according to the present invention comprises an alkali-soluble resin, a fluorescent dye, a photopolymerization initiator, a photopolymerizable compound and a solvent, wherein the alkali- And a glass transition temperature of less than 0 占 폚.
[Chemical Formula 1]
(In the
R 1 is hydrogen, a C 1 to C 12 aliphatic hydrocarbon or a
As described above, the self-luminescent photosensitive resin composition according to the present invention has an effect of providing a color conversion layer having high sensitivity and high efficiency as well as excellent developing speed and adhesion by using an alkali-soluble resin having a specific structure.
Further, the color conversion layer produced using the photosensitive resin composition of the present invention has an excellent effect of fluorescence efficiency and development speed.
1 is a schematic diagram showing the role of a color conversion layer in an image display device.
The self-luminescent photosensitive resin composition according to the present invention includes an alkali-soluble resin, a fluorescent dye, a photopolymerization initiator, a photopolymerizable compound and a solvent.
The alkali-soluble resin contained in the self-luminescent photosensitive resin composition of the present invention contains the following
[Chemical Formula 1]
In
At this time, in the aliphatic hydrocarbon or aromatic hydrocarbon, at least one of the carbon atoms may be substituted with a hetero atom.
The compound represented by the formula (1) may be at least one selected from the group consisting of epoxidized dicyclodecanyl (meth) acrylate, 3,4-epoxytricyclodecan-8-yl (meth) acrylate, 3,4-epoxytricyclodecan- (Meth) acrylate, epoxylated dicyclopentanyloxyethyl (meth) acrylate, 2- (3,4-epoxytricyclodecan-9-yloxy) ethyl (meth) Epoxy tricyclodecan-8-yloxy) ethyl (meth) acrylate, and epoxidized dicyclopentanyloxyhexyl (meth) acrylate.
Particularly preferred are epoxidized dicyclodecanyl (meth) acrylate and epoxidized dicyclopentanyloxyethyl (meth) acrylate.
Here, (meth) acrylate means acrylate or methacrylate, and these may be used alone or in combination of two or more.
Since the self-luminescent photosensitive resin composition of the present invention contains the alkali-soluble resin of the above formula (1), the fluorescence efficiency is always maintained, which is advantageous from the viewpoint of processing.
The alkali-soluble resin is characterized by containing a repeating unit represented by the general formula (2) or (3).
(2)
(In the formula (2)
R 2 and R 3 are each independently a hydrogen atom or a methyl group,
R < 4 > is a residue comprising a carboxylic acid derived by an acid anhydride.
In the above formula (2), the acid anhydride may be selected from the group consisting of phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, Glutaric anhydride, phenyl succinic anhydride, indaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic anhydride and hexahydrophthalic anhydride.
(3)
(3)
R 5 are each independently a hydrogen atom or a methyl group,
And R < 6 > is a C2 to C20 alkyl group.
The compound represented by the general formula (3) may be at least one selected from the group consisting of ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, Butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, , n-pentyl methacrylate, 2-methylbutyl acrylate, 2-methylbutyl methacrylate, 2-ethylpropyl acrylate, 2-methylbutyl methacrylate, n- N-decyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-hexadecyl acrylate, n-hexyl acrylate, n-hexyl acrylate, - Haptadecyl acrylate Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, Ethyl acrylate, ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, Hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, Methoxyethyl acrylate, methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol Methoxypropyleneglycol methacrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxypropylene glycol methacrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; Acrylate, 2-aminoethyl methacrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl methacrylate, 2-dimethylaminopropyl methacrylate, Acrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl arc Acrylate, an unsaturated carboxylic acid aminoalkyl esters such as 3-dimethylaminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; A macromonomer having a monoacryloyl group or monomethacryloyl group at the end of a polymer molecular chain of polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like.
The alkali-soluble resin according to the present invention includes the above-mentioned repeating units and exhibits a glass transition temperature of less than 0 ° C, thereby significantly improving the development speed of the composition and at the same time improving the sensitivity and adhesion, Thereby making it possible to suppress the problem.
In addition, when a pattern is formed using the composition containing the alkali-soluble resin, the step of the pattern which can be enlarged by the colorant in the composition can be minimized, the smoothness can be remarkably improved, and the transmittance can also be improved.
The content of the repeating unit represented by the above-mentioned formula (1) is not particularly limited, but may be, for example, 50 to 90% by weight, preferably 50 to 75% by weight, based on the entire alkali-soluble resin . When the above range is satisfied, it may be more preferable to set the glass transition temperature of the polymerized resin to less than 0 캜. When the repeating unit is contained in an amount of less than 50% by weight, the sensitivity may be lowered and a pattern may be short-circuited. If the repeating unit is contained in an amount exceeding 90% by weight, the storage stability of the resin may be deteriorated .
On the other hand, when the glass transition temperature (Tg) of the polymerized alkali-soluble resin is 0 deg. C or higher, a step may be generated depending on the content of the coloring agent in the composition and it may be difficult to ensure flatness.
The alkali-soluble resin of the present invention may be prepared by copolymerizing a monomer having an unsaturated double bond in addition to the monomer for forming the repeating unit represented by the formula (1).
The monomer having a copolymerizable unsaturated double bond is not particularly limited and specific examples thereof include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Aromatic vinyl compounds such as diesters; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-methylcyclohexyl Alicyclic (meth) acrylates such as mono (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.
These monomers may be used alone or in combination of two or more. The content of the compound having a copolymerizable unsaturated double bond is not particularly limited and may be, for example, 10 to 50% by weight, preferably 30 to 40% by weight, based on the total amount of monomers for polymerizing the alkali- % ≪ / RTI > When the above range is satisfied, the glass transition temperature of the resin is less than 0 DEG C, so that the step can be minimized.
Hereinafter, a method for producing an alkali-soluble resin according to the present invention will be described in more detail.
The alkali-soluble resin of the conventional self-luminescent photosensitive resin composition was prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern. However, the alkali-soluble resin formed by such a production method has a problem that a resin having a carboxyl group in its main chain and having a glass transition temperature of less than 0 캜 is difficult to produce. However, the alkali-soluble resin of the present invention is prepared so that the carboxyl group is contained in the side chain other than the main chain in which the polymerization reaction is carried out, thereby giving proper developing property and exhibiting a glass transition temperature of less than 0 占 폚.
Meanwhile, one embodiment of the production method of the present invention comprises: (S1) copolymerizing glycidyl (meth) acrylate and a monomer having an unsaturated double bond; (S2) reacting the prepared copolymer with an ethylenically unsaturated monomer having a carboxyl group; And (S3) reacting the reacted copolymer with an acid anhydride.
The step (S2) is a step for imparting photo-curability to the alkali-soluble resin of the present invention. In the step (S2), the kind of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited as far as it functions , For example, (meth) acrylic acid, ethyl acrylic acid, butyl acrylic acid and the like, preferably methacrylic acid. The step (S3) is a step for imparting an appropriate acid value to the alkali-soluble resin of the present invention. More specifically, the step (S3) is a step of reacting a hydroxyl group derived from the glycidyl group of the alkali-soluble resin with an acid anhydride, To introduce a carboxyl group.
The acid value of the alkali-soluble resin prepared according to the above-described production method of the present invention may be 30 to 150 mgKOH / g in order to ensure compatibility with the dye contained in the composition and storage stability of the composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, it may be difficult to secure a sufficient development rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, There arises a problem that compatibility with the dye occurs, so that the dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is deteriorated and the viscosity may increase.
The alkali-soluble resin is used in an amount of 1 to 60% by weight, preferably 5 to 50% by weight, based on the total weight of the solid content in the photosensitive resin composition of the present invention. When the amount of the alkali-soluble resin is in the range of 1 to 60% by weight based on the above-mentioned criteria, the solubility is good and the pattern formation is excellent.
The fluorescent dyes contained in the self-luminescent photosensitive resin composition of the present invention can be used as a solvent in a color index (published by The Society of Dyers and Colourists), a solvent, an acid, a basic, dyes classified as reactive, direct, disperse or vat. More specifically, the dyes of the color index (C.I.) number as described below are not limited thereto.
C.I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C.I. Acid Yellow 7, 23, 25, 42, 65, 76;
C.I. Reactive Yellow 2, 76, 116;
C.I. Direct Yellow 4, 28, 44, 86, 132;
C.I. Dispulse Yellow 54, 76;
C.I. Solvent Orange 41, 54, 56, 99;
C.I. Acid Orange 56, 74, 95, 108, 149, 162;
C.I. Reactive Orange 16;
C.I. Direct Orange 26;
C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C.I. Acid Violet 102;
C.I.
C.I.
C.I.
C.I. Bat Green 1st.
Typical fluorescent dyes include 3- (2-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2-benzoimidazolyl) And the like. In addition, naphthalimide dyes such as Solvent Yellow 43, Solvent Yellow 44, and the like may be used. In addition, various low molecular weight light emitting materials and various high molecular weight light emitting materials can be applied
Quinacridone derivatives such as diethylquinacridone (DEQ); The cyanine dye such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM-1, I), DCM-2 (II), and DCJTB ; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4a-diaza-s-indacene (IV), lumogen F red, nile red . Further, it is also possible to use 3- (2-benzothiazolyl) -7-diethylamino coumarin (also referred to as "diethylamino coumarin") Coumarin 6), 3- (2-benzimidazolyl) -7-diethylaminocoumarin (coumarin 7) and coumarin 135; Based low molecular organic fluorescent dyes such as naphthalimide dyes such as Solvent Yellow 43 and Solvent Yellow 44. Alternatively, a polymeric fluorescent material represented by polyphenylene, polyarylene, or polyfluorene may be used as a color conversion dye.
In some cases, a mixture of two or more coloring matters may be used as the color conversion coloring matter. The use of the dye mixture is effective when the wavelength shift width is wide, for example, when converting blue light into red light. The pigment mixture may be a mixture of the above-mentioned pigments. A mixture of the above-mentioned coloring matter and the following coloring matter may also be used. Quinacridone derivatives such as diethylquinacridone (DEQ); (DCM-1), DCM-2 (II), and DCJTB (III), and the like. A cyanine dye; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4-diaza-s-indacene ( IV); Xanthene such as Lumogen F red, Lumogen F orange, Lumogen F yellow, Nile Red (V), rhodamine B, and rhodamine 6G, ) Colored pigments; And pyridine-based pigments such as pyridine-1.
The photopolymerization initiator contained in the self-luminescent photosensitive resin composition of the present invention preferably contains an acetophenone-based compound.
Examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan- And oligomers of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.
In addition, photopolymerization initiators other than the acetophenone-based photopolymerization initiator may be used in combination. Photopolymerization initiators other than acetophenone-based photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals upon irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether and the like. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylphenazine, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- -Propoxyloxanthone, and the like. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) 6,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4 dimethoxyphenyl) ethenyl] -1,3,5- Triazine, and the like. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene sulfone 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, Diphenyl iodonium hexafluoroantimonate and the like, and nitrobenzyl tosylates, benzoin tosylates and the like. Also, as the active radical generator, there are compounds which generate an acid at the same time as an active radical, and for example, a triazine-based photopolymerization initiator is also used as an acid generator.
The content of the photopolymerization initiator used in the colored photosensitive resin composition according to the present invention is usually from 0.1 to 40% by mass, preferably from 1 to 30% by mass, based on the total amount of the binder resin and the photopolymerizable compound based on the solid content . When the amount falls within the above range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion tends to be favorable. Further, in the present invention, a photopolymerization initiator may be used.
The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator, and is a compound used for promoting polymerization of a photopolymerizable compound initiated by a photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.
Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2- , 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (collectively, Michler's ketone), 4,4'- ) Benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. . Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- -Propoxyloxanthone, and the like. Such a photopolymerization initiator may be used alone or in combination of two or more thereof. Commercially available photopolymerization initiators can be used. Examples of commercially available photopolymerization initiators include trade names "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.
When these photopolymerization initiators are used, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. If it is included in the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to be improved.
The photopolymerizable compound contained in the self-luminescent photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers and other polyfunctional monomers. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.
The photopolymerizable compound is used in a mass fraction of usually 5 to 50% by mass, preferably 7 to 45% by mass with respect to the solid content in the self-light-sensitive photosensitive resin composition. When the photopolymerizable compound is contained in the above range, the strength and smoothness of the pixel portion can be improved.
The solvent contained in the self-luminescent photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the colored photosensitive resin composition can be used.
Examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, Alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Acetone, methyl Ketones such as methyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate , Cyclic esters such as? -Butyrolactone, and the like.
The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in the solvent in terms of coating property and drying property, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.
The content of the solvent in the colored photosensitive resin composition of the present invention is 60 to 90% by mass, preferably 70 to 85% by mass, based on the total amount of the colored photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the coating property tends to be improved when the composition is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Therefore, it is desirable.
The self-luminescent photosensitive resin composition of the present invention may further comprise an antioxidant.
The antioxidant may be used alone or in combination of two or more. The antioxidant may be used in an amount of 0.1 to 10% by weight, preferably 0.2 to 7% by weight, based on the solid content in the self-luminescent photosensitive resin composition. Such a content is a range selected to prevent deterioration of light efficiency in a photopolymerization initiator, and is used in a weight ratio within a specific range to a photopolymerization initiator in particular. Preferably, the photostabilizer is used in a range of 1: 0.1 to 1: 3, more preferably 1: 0.2 to 1: 0.5, by weight of a photopolymerization initiator: antioxidant. If the content of the antioxidant and the content of the photopolymerization initiator is less than the above range, the light efficiency can not be ensured and the color conversion property to be obtained in the present invention can not be sufficiently secured. On the other hand, Therefore, it should be adjusted within the above range.
These antioxidants may be selected from the group consisting of benzotriazole light stabilizers, triazine light stabilizers, benzophenone stabilizers, Hals light stabilizers, and combinations thereof, but are not limited thereto.
As the benzotriazole-based light stabilizer, known benzotriazole-based derivatives can be used, and they can be obtained from commercial products. Specific examples include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert- butylphenyl) benzotriazole, 2- Benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole or 2- (2'-hydroxy-3 ', 5' (Commercially available from Tinuvin PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUBIN 571, TINUVIN 900, TINUVIN 928 or TINUVIN 1130 Trade name, manufactured by Chemicals Corporation).
As the triazine light stabilizer, a hydroxyphenyltriazine based ultraviolet absorber is preferable. For example, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 or TINUVIN 1577 (manufactured by Ciba Specialty Chemicals, Ltd., trade name).
As the benzophenone light stabilizer, benzophenone derivatives known as a light stabilizer can be used, and they can be obtained from commercial products. Specific examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- 4-hydroxybenzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy- 2,2'-dihydroxy-4-methoxybenzophenone or 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and commercially available ones include CHIMASSORB81 (available from Ciba Specialty Chemicals, Ltd., trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
The light stabilizers may be used singly or in combination of two or more, preferably in combination with benzotriazole, triazine or benzophenone light stabilizers having a good absorption range at 350 nm or less. Commercially available products may be TINUVIN 5050, TINUVIN 5060, or TINUVIN 5151.
If necessary, the colored photosensitive resin composition of the present invention may contain a filler, other polymer compound, pigment dispersant. An adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like. Specific examples of the filler include glass, silica, alumina and the like. Specific examples of other polymer compounds include curable resins such as epoxy resin and maleimide resin, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane have. As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylpethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Sol SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane and the like. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone. Specific examples of the anti-aggregation agent include sodium polyacrylate.
The colored photosensitive resin composition of the present invention can be produced, for example, by the following method. The dye is dissolved by mixing with the solvent in advance. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin may be blended. The remainder of the binder resin, the photopolymerizable compound and the photopolymerization initiator, the antioxidant, other components to be used if necessary, and, if necessary, the additional solvent are added to the obtained dispersion (hereinafter, also referred to as mill base) To obtain the intended self-luminescent photosensitive resin composition.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
Preparation Example 1: Preparation of alkali-soluble resin A
A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether, and nitrogen in air in a flask to prepare a azobisisobutyl , 3.1 g of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 55.2 g of 2-ethylhexyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate g, and 6.0 g of n-dodecanethiol. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.
After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.
The alkali-soluble resin of Synthesis Example 1 contains all of the structural units represented by the
Production Example 2: Alkali-soluble resin B
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 100 g of propylene glycol monomethyl ether and nitrogen atmosphere in the flask, , 3.1 g of monomethacrylate of tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 38.4 g of n-butyl acrylate, 5.9 g of 4-methylstyrene, 2.5 g of glycidyl methacrylate And 6.0 g of n-dodecanethiol were added thereto. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.
After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air at a nitrogen flow rate, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid and 136 g of propylene glycol monomethyl ether acetate And reacted at 100 DEG C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.
The alkali-soluble resin of Synthesis Example 2 contains all of the structural units of the above-mentioned
Production Example 3: Alkali-soluble resin C
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen atmosphere in air in a flask, , 3.1 g of monomethacrylate of tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 88.8 g of n-hexadecyl acrylate, 5.9 g of 4-methylstyrene, 0.5 g of glycidyl methacrylate , And 6.0 g of n-dodecanethiol were added thereto. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.
After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air at a nitrogen flow rate, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid and 136 g of propylene glycol monomethyl ether acetate And reacted at 100 DEG C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.
The alkali-soluble resin of Synthesis Example 3 contains all of the structural units represented by
Production Example 4: Alkali-soluble resin D
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, and the atmosphere in the flask was replaced with nitrogen in air.
Thereafter, 70.5 g of benzyl methacrylate, 43.0 g of methacrylic acid, 22.0 g of tricyclodecane skeleton mono-methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 136 g of propylene glycol monomethyl ether acetate, And 3.6 g of bisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was stirred at 100 ° C for 5 hours. Subsequently, 35.5 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the mixture was reacted at 110 DEG C for 6 hours.
The alkali-soluble resin of Synthesis Example 4 contained only the structural unit of
Production Example 5: Alkali-soluble resin E
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, and the atmosphere in the flask was replaced with nitrogen in air.
Thereafter, a mixed solution obtained by mixing 70.5 g of benzyl methacrylate, 43.0 g of methacrylic acid, 55.2 g of 2-ethylnapyl acrylate, 136 g of propylene glycol monomethyl ether acetate and 3.6 g of azobisisobutyronitrile was added The mixture was added dropwise to the flask over 2 hours and stirred at 100 ° C for 5 hours.
Subsequently, 35.5 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the mixture was reacted at 110 DEG C for 6 hours.
The alkali-soluble resin of Synthesis Example 5 contained only the structural unit of Formula 2, the solid-dispersibility of the alkali-soluble resin was 61 mgKOH / g, and the weight-average molecular weight Mw by GPC was 8,310.
Examples 1 to 3 and Comparative Examples 1 to 2
2) HALS light stabilizer (manufactured by Ciba Specialty Chemicals)
3) HALS-based / benzotriazole-based blend light stabilizer (available from Ciba Specialty Chemicals)
4) The alkali-soluble resin of Synthesis Example 1
5) The alkali-soluble resin of Synthesis Example 2
6) The alkali-soluble resin of Synthesis Example 3
7) The alkali-soluble resin of Synthesis Example 4
8) The alkali-soluble resin of Synthesis Example 5
9) Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
10) 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, product of Ciba Specialty Chemicals
11) Propylene glycol monomethyl ether acetate
Color Filter Color Conversion Layer (Color Conversion Pixel: Glass Substrate) Manufacturing Example
A color filter was prepared using the self-luminescent photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2. That is, each of the self-luminescent photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. Then, the thin film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Usuo Denki Co., Ltd., and no special optical filter was used. The ultraviolet-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 for 60 seconds using a spray developing machine and heated in a heating oven at 220 ° C for 20 minutes to prepare a pattern. The film thickness of the self-emission color conversion layer pattern prepared above was 3.0 mu m. The thickness of the color conversion layer can be controlled to various values up to 500 mu m.
1. Measurement of luminescence intensity
The self-emission color pattern having a thickness of 3.0 mu m prepared using the self-luminescent photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 was measured with a quantum efficiency meter (QE-1000, manufactured by Otsuka) The luminescence PL of the coated substrate was measured, and the luminescence intensity was described in Table 2 below. At this time, the higher the emission intensity measured, the better the luminance characteristic.
As can be seen from the above Table 2, the luminescence intensity values of Examples 1 to 3 were 13000 on average, and the luminescence intensities were higher than those of Comparative Examples 1 and 2.
2. Evaluation of heat resistance
A color filter was prepared using the photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2. Specifically, each of the photosensitive resin compositions was coated on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film .
Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used.
The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, and then blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 mu m.
Heat resistance
The heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230 ° C. for 120 minutes. △ Eab is the value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (New Color Science Handbook (1986) p.266).
? E * ab = {(? L) 2 + (? A) 2+ (? B) 2} 1/2
[Criteria for evaluation of heat resistance]
∘: ΔE * ab value: not more than 3
Δ: ΔE * ab value: 3 to 10 or less
X: DELTA E * ab value: exceed 10
Development speed and residue evaluation
Each of the self-luminescent photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. The film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; Veeco). After the thickness measurement was completed, the substrate was again immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop, and then the remaining self-light-sensitive resin composition was confirmed in the unexposed portion.
[Development rate evaluation criteria]
The time taken for the unexposed area to completely dissolve in the developing solution was measured and shown. If the development is not possible, it is indicated by 'X'.
[Residue evaluation criteria]
O: If not remaining
?: Remained above 0% to below 20%
X: 20% or more remains
Referring to Table 3, it can be seen that Examples 1 to 3 have excellent surface characteristics of the coating film and have a high developing speed. In addition, there is no residue, and since it has excellent heat resistance, it can be seen that the quality is excellent.
On the other hand, in the case of Comparative Examples 1 and 2, the surface properties of the coating film were not excellent, and the developing rate, residue and heat resistance were not excellent.
1: substrate
3: color conversion layer
5: Color filter
Claims (8)
The alkali-soluble resin
1. A self-luminescent photosensitive resin composition comprising the following formula (1) and having a glass transition temperature of less than 0 占 폚:
[Chemical Formula 1]
(In the formula 1,
R 1 is hydrogen, a C 1 to C 12 aliphatic hydrocarbon or a C 1 to C 12 aromatic hydrocarbon.
The alkali-soluble resin
A self-luminescent photosensitive resin composition comprising a repeating unit represented by the following formula (2) or (3):
(2)
(In the formula (2)
R 2 and R 3 are each independently the same or different and represent hydrogen or a methyl group,
R < 4 > is a residue comprising a carboxylic acid derived by an acid anhydride.
(3)
(3)
R < 5 > each independently represent hydrogen or a methyl group,
And R < 6 > is an alkyl group of C2 to C20.
With respect to the solid content in the self-luminescent photosensitive resin composition,
Wherein the photopolymerization initiator comprises 0.1 to 10% by weight of the fluorescent dye, 1 to 60% by weight of an alkali-soluble resin and 5 to 50 parts by weight of a photopolymerizable compound, wherein the photopolymerization initiator is present in an amount of 0.1 to 40 wt% % Of the self-luminescent photosensitive resin composition.
Wherein the self-luminescent photosensitive resin composition further comprises an antioxidant.
Wherein the antioxidant is a phenol-based, phosphorus-based, or sulfur-based antioxidant.
The antioxidant
Wherein the self-luminescent photosensitive resin composition contains 0.1 to 10% by weight based on the solid content of the self-luminescent photosensitive resin composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180090541A (en) | 2017-02-03 | 2018-08-13 | 동우 화인켐 주식회사 | Self Emission Type Photosensitive Resin Composition, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
| KR20190061808A (en) | 2017-11-28 | 2019-06-05 | 동우 화인켐 주식회사 | Photosensitive Resin Composition for Color Conversion Layer, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
| KR20190061813A (en) | 2017-11-28 | 2019-06-05 | 동우 화인켐 주식회사 | Photosensitive Resin Composition for Color Conversion Layer, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
| KR20210095313A (en) | 2020-01-23 | 2021-08-02 | 동우 화인켐 주식회사 | Self emission type photosensitive resin composition, color filter comprising color conversion layer using the same and display device |
| TWI789368B (en) * | 2016-11-15 | 2023-01-11 | 南韓商東友精細化工有限公司 | Photosensitive resin composition, color filter and image display device |
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| KR20190061808A (en) | 2017-11-28 | 2019-06-05 | 동우 화인켐 주식회사 | Photosensitive Resin Composition for Color Conversion Layer, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
| KR20190061813A (en) | 2017-11-28 | 2019-06-05 | 동우 화인켐 주식회사 | Photosensitive Resin Composition for Color Conversion Layer, Color Filter Comprising Color Conversion Layer Using the Same and Display Device |
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