TW201631395A - Self-emission type photosensitive resin composition, and display device comprising color conversion layer prepared thereof - Google Patents

Abstract

The present invention relates to a self-emission type photosensitive resin composition, and a display device comprising a color conversion layer made of the resin composition, more particularly, it relates to a self-emission type photosensitive resin composition containing a fluorescent dye, a photopolymerizable compound, an oxime ester photopolymerization initiator, a binder resin, and a solvent. Also disclosed is a display device comprising a color conversion layer made of the resin composition. The color conversion layer containing said composition can solve problems of lower optical efficiency caused by the existing color filters and lower optical efficiency due to the photoinitiator, as well as the problem caused by the yellowing. High brightness is maintained and excellent color conversion characteristics and high optical efficiency are ensured by introducing the composition into a display device, thereby realizing a sharp picture quality of high-grade.

Description

Self-luminous photosensitive resin composition, display device containing the color conversion layer produced therefrom Field of invention

The present invention relates to a self-luminous photosensitive resin composition capable of achieving high-quality image quality by ensuring excellent color conversion characteristics and high fluorescence efficiency, and a display device including the color conversion layer produced therefrom.

Background of the invention

The recent display industry is rapidly changing from flat panel displays represented by CRTs (cathode ray tubes) to PDPs (plasma display panels), OLEDs (organic light-emitting diodes), and LCDs (liquid crystal displays). Among them, LCD is widely used in image display devices used in almost all industries, and its application range continues to expand.

The LCD adjusts the transmittance while the white light generated by the backlight unit passes through the liquid crystal cell, and mixes the three primary colors that pass through the red, green, and blue color filters to achieve full color.

As a light source of the backlight unit, a CCFL (Cold Cathode Fluorescent Lamp) is used, but in this case, the backlight unit must always apply power to the CCFL, thus causing a problem of power consumption. In addition, compared with the existing CRT, the problem of color reproduction rate of about 70% level and environmental pollution caused by adding mercury is disadvantaged. Point out.

As a substitute for solving the above problem, research on a backlight unit using an LED (Light Emitting Diode) has been actively conducted. In the case of using LEDs as backlight units, 100% higher than the NTSC (National Television System Committee) color reproduction range specification can provide consumers with more vivid image quality.

Therefore, in the same industry, in order to improve the efficiency of the backlight source, a method of changing the material and structure of the color filter and the LCD panel has been proposed.

After the color filter is applied with a dispersion composition containing a pigment or a dye, pixels of various colors are formed by a patterning process, but such pigments and dyes cause a problem of lowering the transmission efficiency of the backlight source. As a result of the decrease in the transmission efficiency, the color reproducibility of the display device is lowered, and as a result, it is 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. Therefore, a method of increasing the thickness of the color filter or introducing a color conversion layer (or a light conversion layer) thereon or in close proximity thereto has been proposed.

1 is a schematic view showing the action of a color conversion layer in a display device. As shown in FIG. 1, a light source generated by the backlight 1 can directly increase light efficiency through the color conversion layer 3 and the color filter 5.

Conventional dyes and pigments are used for the composition of the color conversion layer. However, it is difficult to expect an improvement in light efficiency by using such dyes and pigments, and conversely, there is a problem that brightness is lowered. Therefore, a substance using a fluorescent substance as the color conversion layer 3 has been proposed.

The fluorescent substance is excited by the blue light emitted by the backlight 1 to make the blue The wavelength of light changes and emits light in the front direction, and white light such as red white light or green white light is emitted, and as a result, light efficiency is improved.

A large number of patents are proposed for a color conversion layer having a fluorescent substance, wherein the display device has a light conversion portion, which is disposed in a backlight unit and a substrate, in the Korean Patent Publication No. 2012-0048218 Arranged between the upper portion of the shutter portion and at least one fluorescent material that converts incident light of a blue or ultraviolet wavelength band into light of a predetermined wavelength band.

Korean Patent Publication No. 2013-0083807 proposes a liquid crystal display device including a backlight unit for improving light efficiency. In this case, in order to improve light efficiency, it is shown that a phosphor, a quantum dot (Quantum Dot), a white scatterer, and an electrophoresis are introduced. A color conversion substance such as an electroluminescence substance or a photoluminescence material.

In order to increase the brightness of a white light-emitting diode (LED), a method of introducing a color conversion layer composed of a green light-emitting phosphor is shown in Japanese Laid-Open Patent Publication No. 2013-077825.

These patents seek to improve the quality of a display device by introducing a color conversion layer containing a phosphor or the like. However, at this time, the formation method of the color conversion layer is not directly mentioned, and even if it is mentioned, it is only shown that it is simply dispersed in a solvent. The method of wet coating in the middle and the middle.

As shown in FIG. 1, the color conversion layer can be formed into a pattern corresponding to the red R and green G pixel portions of the color filter, respectively, but at this time, the phosphor of several hundred micrometers for the color conversion layer is not dissolved. Since it is in a state of being dispersed in a solvent, it is difficult to realize a fine pattern, and it is difficult to adjust physical properties such as thickness.

Such difficulty can be solved by realizing a fine pattern by photolithography using a photosensitive resin composition.

In the case of a usual photosensitive resin composition, it is necessary to use a photoinitiator for polymerization, but not only the fluorescence efficiency of the phosphor is lowered by the radical generated by the photoinitiator, but also in the photolithography process. In the post-baking process performed in the middle, a new problem such as yellowing of the color conversion layer by the photoinitiator is caused.

Prior art literature

Patent literature

Patent Document 1: Korean Patent Publication No. 2012-0048218

Patent Document 2: Korean Patent Publication No. 2013-0083807

Patent Document 3: Japanese Patent Laid-Open No. 2013-077825

Summary of invention

The present invention has been made to solve the above problems, and provides a self-luminous photosensitive resin composition which exhibits excellent color conversion characteristics by using a specific photopolymerization initiator at a specific content. The high fluorescence efficiency improves the development speed and adhesion by containing a specific binder resin.

Further, another object of the present invention is to provide a display device which can realize a high-quality vivid image by having a color conversion layer containing the self-luminous photosensitive resin composition.

In order to achieve the above object, the present invention relates to a method for forming a color conversion layer. The composition contains a fluorescent dye, an antioxidant, a binder resin, a photopolymerizable compound, an oxime ester photopolymerization initiator, and a solvent.

Further, the present invention relates to a display device comprising a color conversion layer produced using the self-luminous photosensitive resin composition.

The self-luminous photosensitive resin composition according to the present invention can solve the problem of a decrease in light efficiency caused by a color filter, a decrease in light efficiency caused by a photoinitiator, and a yellowing.

The display device in which the color conversion layer produced by the self-luminous photosensitive resin composition is introduced maintains high luminance, and ensures excellent color conversion characteristics and high light efficiency, thereby achieving high-quality vivid image quality.

1‧‧‧Substrate

3‧‧‧Color conversion layer

5‧‧‧Color filters

Fig. 1 is a schematic view showing the action of a color conversion layer in a display device.

Detailed description

The present invention shows a self-luminous photosensitive resin composition which can be used for a color conversion layer of a display device.

The color conversion layer is located adjacent to the color filter (see FIG. 1) in order to improve the reduced light efficiency due to the use of the color filter, and is made of a fine pattern in a manner corresponding to the red R and green G patterns of the color filter. Composition.

Hereinafter, the self-luminous photosensitive resin composition will be described in detail.

The present invention contains a fluorescent dye, a photopolymerizable compound, a photopolymerization initiator, a binder resin, and a solvent.

Particularly in the present invention, it is shown that the composition of the color conversion layer contains A photosensitive resin composition containing a photo-dye and a specific photopolymerization initiator as an essential component, the fluorescence efficiency by the self-distribution of the above-mentioned fluorescent dye brings about an improvement in overall light efficiency, and the photosensitive resin composition can form a fine pattern. The high-sensitivity photopolymerization initiator ensures the effect of preventing a decrease in the fluorescence efficiency.

More specifically, the oxime ester-based initiator of the diphenyl sulfide structure or the oxime ester-based initiator of the carbazole structure of the present invention has a high sensitivity and can achieve a sufficient curing rate in a small amount, thereby suppressing the fluorescence efficiency. reduce.

The self-luminous photosensitive resin composition of the present invention contains a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent together with the above-mentioned fluorescent dye.

Hereinafter, each component will be described.

The fluorescent dye contained in the self-luminous photosensitive resin composition of the present invention is classified into a solvent (Solvent) and acid in a Colour Index [The Society of Dyers [0119] and Colourists Publishing]. (Acid), Basic, Reactive, Direct, Disperse, or Reduced (Vat) dyes. More specifically, a dye having a color index (C.I.) number as described below may be mentioned, but is not limited thereto.

CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI disperse yellow 54, 76; CI solvent orange 41, 54, 56, 99; CI acid orange 56, 74, 95, 108, 149, 162; CI active orange 16; CI direct orange 26; CI solvent red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI acid red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 102; CI Solvent Green 1, 5; CI Acid Green 3, 5, 9, 25, 28; CI Alkaline Green 1; CI Reducing Green 1 and the like.

As a general fluorescent dye, it contains 3-(2-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6), 3-(2-benzimidazolyl)-7-diethyl Coumarin dyes such as hydroxycoumarin (coumarin 7) and coumarin 135. Further, a naphthylquinone imine dye such as Solvent Yellow 43 or Solvent Yellow 44 may also be used. In addition, various low molecular light-emitting materials and various polymer light-emitting materials can also be applied.

Containing a quinacridone derivative such as diethyl quinacridone (DEQ); 4-dicyanomethylidene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyridyl Cyanine pigments such as DCM-1, (I), DCM-2 (II), and DCJTB (III); 4,4-difluoro-1,3,5,7-tetraphenyl-4-boron Hetero-3a, 4a-diaza-s-inducing province (IV), Luma near F red, Nile red (V) and the like. Further, a xanthene dye such as rhodamine B or rhodamine 6G or a pyridine dye such as pyridine 1 may be used, and 3-(2-benzothiazolyl)-7-diethylaminoxiang may be contained. Beans (diethylamino coumarin) (coumarin 6), 3-(2-benzimidazolyl)-7-diethylaminocoumarin (coumarin 7), coumarin 135, etc. Prime pigment A low molecular weight organic fluorescent pigment such as a solvent such as Solvent Yellow 43 or Solvent Yellow 44. Alternatively, a polymer fluorescent material represented by polyphenylene, polyarylene or polyfluorene may be used as the color conversion dye.

Depending on the case, a mixture of two or more kinds of dyes may be used as the color conversion dye. The use of the dye mixture is an effective means when the wavelength shift width is wide as in the case of conversion from blue light to red light. The pigment mixture may be a mixture between the above pigments. Further, a mixture of the above dye and the following dye may be used. Preferred are quinacridone derivatives such as diethylquinacridone (DEQ); 4-dicyanomethylene-2-methyl, (dimethylaminostyryl) )) 4H-pyran (DCM-1, (I)), DCM-2 (II), and DCJTB (III) and other cyanine pigments; 4,4-difluoro-1,3,5, 7-tetraphenyl-4-bora(bora)-3a,4a-diaza-s-inducence (IV); Lumogen F red, road Lumogen F orange, Lumogen F yellow, Nile Red (V), rhodamine B, rhodamine 6G and other xanthene pigments; And a pyridine-based dye such as pyridine 1.

The fluorescent dye may be contained in an amount of 0.1 to 30% by weight, preferably 0.1 to 20% by weight based on the total weight of the self-luminous photosensitive resin composition.

When the fluorescent dye is contained in the above range, no problem is caused in the pattern formation of the color conversion layer, and sufficient light efficiency can be expected.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is polymerizable by the action of light and a photopolymerization initiator to be described later. The compound may, for example, be a monofunctional monomer, a bifunctional monomer or another polyfunctional monomer. Specific examples of the monofunctional monomer include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and acrylic acid 2- Hydroxyethyl ester, N-vinylpyrrolidone, and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. And triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like. Specific examples of the other polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol-5 ( Methyl) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Among these, a bifunctional or more polyfunctional monomer is preferably used.

The photopolymerizable compound is used in an amount of 5 to 60% by weight, preferably 7 to 50% by weight, based on the total weight of the solid content of the self-luminous photosensitive resin composition. When the photopolymerizable compound is contained in the above range, the strength and smoothness of the pixel portion are improved.

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention contains an oxime ester photopolymerization initiator as an essential component. The oxime ester-based photopolymerization initiator may be one or more selected from the group consisting of the compounds represented by the following Chemical Formulas 1 to 9.

[Chemical Formula 1]

(In the above Chemical Formula 1, R ₁ is -R ₄ -R ₅ , in which case R ₄ is an alkylene group having 1 to 4 carbon atoms, and R ₅ is an alkyl group having 3 to 8 carbon atoms or a cycloalkyl group, R ₂ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ₃ is a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms substituted by an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or Diphenyl sulfide group.)

(In the above Chemical Formula 2, R ₆ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ₇ is -R ₈ -R ₉ . In this case, R ₈ is an alkylene group having 1 to 4 carbon atoms; R ₉ It is an alkyl or cycloalkyl group having a carbon number of 3 to 8.)

(In the chemical formula 3, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁₀ to R ₁₂ each independently represent -R, -OR, -COR, -SR, -CONRR', or -CN In this case, R and R' represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 5- to 7-membered heterocyclic group. One or more substitutions selected from the group consisting of a halogen atom and a 5- to 7-membered heterocyclic group, wherein the alkylene group of the alkyl group and the aralkyl group may be an unsaturated bond, an ether bond, or a thioether bond. The ester bond is interrupted, and R and R' may form a ring together, and R ₁₃ to R ₁₆ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and X is a halogen atom or a carbon atom number of 1. The alkyl group of ~8, Y ¹ to Y ³ are each independently S, O, or Se, m represents an integer of 0 to 4, p represents an integer of 0 to 5, and q represents 0 or 1.

Preferably, in the above Chemical Formula 1, examples of the alkyl group represented by R and R' include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tertiary group. Butyl, pentyl, isopentyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, decyl, isodecyl, decyl, isodecyl, Vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy Ethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, A 2-(benzoxazole-2'-yl)vinyl group or the like, and among them, an alkyl group having 1 to 8 carbon atoms is preferable.

Further, examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthyl group, and a phenanthrenyl group. Among them, an aryl group having 6 to 12 carbon atoms is preferable. Further, examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group. An aralkyl group having 7 to 13 carbon atoms such as a phenylvinyl group. The heterocyclic group represented by R and R' may, for example, be preferably a heterocyclic group having 5 to 7 carbon atoms such as a pyridyl group, a pyrimidinyl group, a furyl group or a thienyl group. Further, examples of the ring which R and R' may form together include a ring having 5 to 7 carbon atoms such as a piperidine ring or a morpholine ring. Further, R and R' may be substituted by a halogen element such as fluorine, chlorine, bromine or iodine, or may be a pyridyl group, a pyrimidinyl group, a furyl group, a benzoxazol-2-yl group, a tetrahydropyranyl group or a pyrrolidinyl group. (pyrrolidyl), imidazolyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isooxazolidyl, piperidinyl (piperidyl), piperadyl, morpholinyl and the like are substituted with a heterocyclic group having 5 to 7 carbon atoms.

Examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine. Further, the alkyl group represented by X may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group or a pentyl group which is substituted or unsubstituted with a halogen atom. , isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl.

In the above Chemical Formula 3, examples of the halogen atom represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include fluorine, chlorine, bromine and iodine.

Further, in the above Chemical Formula 3, the alkyl group represented by R ₁₆ , R ₁₇ , R ₁₈ or R ₁₉ may be a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group substituted or unsubstituted with a halogen atom. , isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl.

The oxime ester compound of the present invention represented by the above Chemical Formula 3 is preferably a compound described below.

Commercially available products having the chemical formula 3 include N-1919 (ADEKA Co., Ltd.) and the like.

(In the above Chemical Formula 4, R ₁₇ to R ₂₆ are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 7 An arylalkyl group of ~40, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms.

The above R ₁₇ ~ R _{26 may} specifically be hydrogen, bromine, chlorine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, iso Amyl, n-hexyl, isohexyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, fluorenyl, phenanthryl, methoxy, ethoxy, n-propoxy, isopropoxy, n-Butoxy, isobutoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-n-butyl, hydroxyisobutyl, hydroxy-n-pentyl, hydroxyisopentyl, hydroxy-n-hexane Base, hydroxyisohexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, hydroxyethyl Oxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl, or hydroxyethoxyhexyl.

Preferably, R ₁₇ is hydrogen, methyl, ethyl, propyl or butyl; R ₁₈ is methyl, ethyl or propyl; R ₁₉ is methyl, ethyl, propyl or butyl ; R ₂₀ ~ R ₂₆ may be hydrogen.

The ruthenium-based initiator used in the present invention is typically a compound described below, but is not limited to the following examples, and any compound known in the art as a compound satisfying the above conditions can be used.

(In the chemical formula 5, R ₂₇ is (II), n is an integer of 1 to 4, m is an integer of 1 to 6, R ₂₈ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ₂₉ is . )

(In the chemical formula 6, X represents a halogen atom or an alkyl group, and R ₃₀ , R ₃₁ and R ₃₂ each independently represent R, OR, COR, SR, CONRR', or CN, and R and R' represent an alkyl group, an aromatic group. a group, an aralkyl group, or a heterocyclic group, which may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, wherein the alkylene group of the alkyl group and the aralkyl group may be unsaturated The bond, the ether bond, the thioether bond, and the ester bond are interrupted, and R and R' may form a ring together. Y ¹ represents an oxygen atom, a sulfur atom, or a selenium atom, A represents a heterocyclic group, and m represents an integer of 0-4. , p represents an integer from 0 to 5, and q represents 0 or 1.)

(In the above Chemical Formula 7, R ₃₃ , R ₃₄ , R ₃₅ , X, Y ¹ , m, p and q are the same as the above Chemical Formula 6, and R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ each independently represent a hydrogen atom, A halogen atom or an alkyl group, and Y ² and Y ³ each independently represent an oxygen atom, a sulfur atom, or a selenium atom.)

(In the above Chemical Formula 8, R ₄₀ , R ₄₁ , R ₄₂ , X, Y ¹ , m, p and q are the same as the above Chemical Formula 6, X' represents a halogen atom or an alkyl group, and r represents an integer of 0-4.)

(In the above Chemical Formula 9, R ₄₃ , R ₄₄ , R ₄₅ , X, Y ¹ , m, p and q are the same as the above Chemical Formula 6, X′′ represents a halogen atom or an alkyl group, and s represents an integer of 0 to 4.)

In addition, a photopolymerization initiator other than the above may be used in combination in a range that does not impair the effects of the present invention. Typically, one or more compounds selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, and thioxanthone-based compounds are preferably used.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. , 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4) -Methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2 -hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)- 1-(4-morpholinophenyl)butan-1-one and the like.

Examples of the benzophenone-based compound include benzophenone, methyl 0-benzylidenebenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. A thioether, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone or the like.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4. - bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3 ,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyrene 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-[2-(4-Diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(3,4-Dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis ( 2,3-Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2 - bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or phenyl group at the 4,4',5,5' position An alkoxycarbonyl substituted imidazole compound or the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) is preferably used. -4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1, 2'-biimidazole.

As the above thioxanthone-based compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythiophene Tons of ketone and so on.

The self-luminous photosensitive resin composition according to the present invention may further contain a photopolymerization initiation aid. In the self-luminous photosensitive resin composition of the present invention, the photopolymerization initiation aid is additionally contained, and the sensitivity is further increased, and the productivity can be improved.

For the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

As the above amine compound, an aromatic amine compound is preferably used. Specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate or the like can be used. Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N - dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthio Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, and 1,3,5-tri ( 3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), and the like.

The photopolymerization initiator may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the content of the photopolymerizable compound and the binder resin, based on the solid content.

When the photopolymerization initiator is contained in the above range, the self-luminous photosensitive resin composition is highly sensitive and the exposure time is shortened. It is high and can maintain high resolution, so it is preferable. Moreover, the intensity of the pixel portion formed using the composition under the above conditions and the smoothness in the surface of the above-described pixel portion become good.

In addition, when the photopolymerization initiation auxiliary agent is further contained, the photopolymerization initiation auxiliary agent may contain 0.1 to 40 parts by weight based on 100 parts by weight of the total of the content of the photopolymerizable compound and the binder resin, based on the solid content. The parts by weight preferably contain 1 to 30 parts by weight. In addition, when the amount of the photopolymerization initiation auxiliary agent used is in the range of 0.1 to 40 parts by weight, the effect of the self-luminous photosensitive resin composition is further increased, and the color filter formed using the above composition is provided. Increased productivity.

The binder resin contained in the self-luminous photosensitive resin composition of the present invention usually has reactivity and alkali solubility due to the action of light and heat, and functions as a dispersion medium for the coloring material. The binder resin contained in the self-luminous photosensitive resin composition of the present invention functions as a binder resin with respect to the fluorescent dye as long as it is soluble in the alkaline phase used in the development stage for producing the color filter. The developer resin of the developer can be used.

The binder resin contained in the self-luminous photosensitive resin composition of the present invention may be a copolymer containing one or more repeating units of the following Chemical Formula 10. Preferably, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer may be mentioned.

[Chemical Formula 10]

(In Chemical Formula 10, R ₄₆ , R ₄₇ , R ₄₈ and R ₄₉ are each independently hydrogen, a halogen group, a C1 to C10 alkyl group; a C5 to C10 cycloalkyl group; or a C6 to C20 aryl group. At this time, the aryl group may be substituted with N, O, or S, and n is 0 or 1.)

The halogen mentioned in the present invention is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

The alkyl group referred to in the present invention contains a linear or branched form, and includes, as an example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, Is n-hexyl, n-octyl, n-decyl and the like.

The cycloalkyl group referred to in the present invention includes a cyclopropyl group, a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a substituted and unsubstituted borneol group, a norbornyl group, a norbornene group, and the like.

The aryl group mentioned in the present invention includes a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group and the like.

In this case, the binder resin may contain all repeating units in which n is 1 and repeating units in which n is 0, and a repeating unit in which n is 1 polymerizes a monomer of the following chemical formula 11, and a repeating unit in which n is 0 will be described below. The monomer of Chemical Formula 12 is polymerized and will be described in detail below.

By the binder resin of Chemical Formula 10 containing the pyran or furan structure as described above, the developing speed is increased, which is advantageous in terms of the process.

In the above binder resin, the content ratio of the repeating unit of Chemical Formula 10 is 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 25 to 40% by weight based on the total weight of the binder resin. If it is in the above range, it has the advantage of adhesion and permeability.

In this case, Chemical Formula 10 can be represented by polymerizing one or more monomers of Chemical Formula 11 and Chemical Formula 12.

(In the chemical formula 11, R ₅₀ , R ₅₁ , R ₅₂ and R ₅₃ are each independently hydrogen, a halogen group, a C1 to C10 alkyl group; a C5 to C10 cycloalkyl group; or a C6 to C20 aryl group. At this time, the aryl group may be substituted with N, O, or S.)

As an example, in the embodiment of the present invention, a substance satisfying the structure of Chemical Formula 11 or a commercially available product can be directly produced and used, and it can be used as a methyl-2-(bromomethyl)-acrylate (product of Aldrich Co., Ltd.). It is obtained by polymerization of triethylamine (product of Aldrich Co., Ltd.) and methyl-2-(hydroxymethyl)-acrylate (product of Aldrich Co., Ltd.). As the solvent to be used in the above polymerization, propylene glycol methyl ether (product of TCI Corporation), 2,2'-azobisisobutyronitrile (product of Wako Co., Ltd.), or the like can be used.

[Chemical Formula 12]

(In the above Chemical Formula 12, R ₅₄ , R ₅₅ , R ₅₆ and R ₅₇ are each independently hydrogen, a halogen group, a C1 to C10 alkyl group; a C5 to C10 cycloalkyl group; or a C6 to C20 aryl group. At this time, the aryl group may be substituted with N, O, or S.)

The copolymer containing the repeating unit of the above Chemical Formula 12 can be polymerized by a method such as the above Chemical Formula 11 using a substituted or unsubstituted dihydrofuran or the like, and such a material can be directly produced or purchased using a commercially available product.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxyl groups in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid.

Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester thereof, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and succinic acid mono (2-methacryloxyethyl)ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate, etc. . The unsaturated polycarboxylic acid can also be a single of its two terminal dicarboxy polymer Examples of the (meth) acrylate include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

These carboxyl group-containing monomers may be used alone or in combination of two or more. Examples of the other monomer copolymerizable with the above carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o. Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl An aromatic vinyl compound such as benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, hydrazine; methyl acrylate, methyl methacrylate, ethyl acrylate, A Ethyl acrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, methacrylic acid Butyl ester, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, C Acid 3-hydroxypropyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, acrylic acid 4 -hydroxybutyl ester, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzene acrylate Ester, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy Diethylene glycol acrylate, Methoxydiglycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxy Dipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, (meth)acrylic acid Adamantyl ester, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, monomethyl glycerol Unsaturated carboxylic acid esters such as acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, acrylic acid 2 -Aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-amino propyl methacrylate Ester, 3-dimethylaminopropyl acrylate, 3-dimethylamino methacrylate Aminoalkyl esters of unsaturated carboxylic acids such as esters; glycidyl esters of unsaturated carboxylic acid such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Vinyl esters such as esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, metacyanic acid A vinyl cyanide compound such as ethylene; acrylamide, methacrylamide, α-chloropropenylamine, N-2-hydroxyethyl decylamine, N-2-hydroxyethyl methacrylamide, etc. Saturated amides; unsaturated imidamines such as maleic imine, benzyl maleimide, N-phenyl maleimide, N-cyclohexylmaleimide; Aliphatic conjugated dienes such as butadiene, isoprene, chloroprene, and polystyrene, polymethyl acrylate, A macromonomer of polymethyl methacrylate, n-butyl polyacrylate, n-butyl methacrylate, polyoxymethane having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end of a polymer branching chain. Wait.

These monomers may be used alone or in combination of two or more. In particular, as another monomer copolymerizable with the above carboxyl group-containing monomer, a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton exists to make a relative dielectric The tendency to decrease the constant value is preferable.

These monomers may be used alone or in combination of two or more. In the case where the above binder resin is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer, the content ratio of the structural unit derived from the above carboxyl group-containing monomer is relative to the structure constituting the above copolymer The total content of the unit is from 10 to 50% by weight, preferably from 15 to 40% by weight, more preferably from 25 to 40% by weight, based on the weight ratio. When the content ratio of the structural unit derived from the carboxyl group-containing monomer is 10 to 50% by weight based on the above-mentioned basis, the solubility in the developer is good, and a pattern is accurately formed during development, which is preferable. Further, the content of the other monomer copolymerizable with the carboxyl group-containing monomer is from 10 to 50% by weight, preferably from 15 to 40% by weight, based on the total amount of the structural unit constituting the above copolymer, more preferably It is 25 to 40% by weight.

The binder 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 self-luminous photosensitive resin composition of the present invention. When the binder resin is contained in the range of 1 to 60% by weight based on the above criteria, solubility is good and pattern formation is excellent, which is preferable.

As the binder resin of the present invention, the acid value is preferably in the range of 20 to 200 (KOH mg/g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion remains at the time of development to improve the film remaining ratio, which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1 g of the acrylic polymer, and can be usually determined by titration using a potassium hydroxide aqueous solution. Further, it is preferable that the polystyrene-equivalent weight average molecular weight (hereinafter referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. Resin. When the molecular weight is in the above range, the hardness of the coating film is increased, the residual film ratio is high, the solubility in the non-exposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin is preferably from 1.5 to 6.0, more preferably from 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is from 1.5 to 6.0, the developability is excellent, which is preferable.

The solvent contained in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the self-luminous photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like, and ethylene glycol monoalkyl ethers. Diethylene glycol dialkyl ethers such as alcohol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl Ethylene glycol alkyl ether acetate such as cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Alkylene glycol alkyl ether acetates such as acid esters, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, benzene, toluene, xylene, Aromatic hydrocarbons such as mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexane An alcohol such as an alcohol, ethylene glycol or glycerin, an ester such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate; or a cyclic ester such as γ-butyrolactone. Among the above-mentioned solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of 100 ° C to 200 ° C is preferable, and an alkylene glycol alkyl ether acetate or a ketone is more preferable. Further, an ester such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may further preferably be propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or cyclohexane. Ketone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the self-luminous photosensitive resin composition of the present invention is usually 60 to 90% by weight, and preferably 70 to 85% by weight based on the total weight of the self-luminous photosensitive resin composition.

When the content of the solvent is within the above range, a coating device such as a roll coater, a spin coater, a slit spin coater, a slit coater (also referred to as a press coater), or an ink jet is used. At the time of coating, the coatability became good.

In the self-luminous photosensitive resin composition of the present invention, additives such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration agent may be used in combination as needed. Specific examples of the filler include glass, cerium oxide, aluminum oxide, and the like. Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl group. A thermoplastic resin such as acrylate, polyester or polyurethane. As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include an anthraquinone surfactant, a fluorine surfactant, an ester surfactant, a cationic surfactant, an anionic surfactant, and a non-aqueous surfactant. Surfactants such as ionic surfactants and amphoteric surfactants. These can be used individually or in combination of 2 or more types. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and uncles. Amine-modified urethanes, polyethyleneimines, and the like, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.), (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), (EFTOP) (made by Tohkem Products), (MEGAFAC) (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), (Flourad) (manufactured by Sumitomo 3M Co., Ltd.), (Asahi guard), (Surflon) (above is manufactured by Asahi Glass Co., Ltd.), (SOLSPERSE) (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like. Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, and N-(2-aminoethyl). -3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropyl Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like. . Specific examples of the anti-agglomerating agent include sodium polyacrylate.

The self-luminous photosensitive resin composition of the present invention can be produced, for example, by the method described below. The dye is previously dissolved in a solvent to dissolve it. At this time, a pigment dispersing agent is used as needed, and some or all of the binder resin may be blended. Further, the remaining binder resin (hereinafter also referred to as a polishing base) is further added with a remaining binder resin, a photopolymerizable compound, a photopolymerization initiator, other components used as necessary, and a solvent added as needed. This is a predetermined concentration, and the target self-luminous photosensitive resin composition is obtained.

The present invention will be described in more detail based on the examples below, but is merely illustrative, and the scope of the invention is not limited to the embodiments. The scope of the present invention is intended to be embraced by the scope of the claims In addition, the "%" and "part" which show the content below are the mass basis unless it demonstrates especially.

Synthesis Example 1. Adhesive Resin B1

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared, and on the other hand, 74.8 g (0.20 mol) of benzyl maleimide and 43.2 g of acrylic acid were charged as a monomer dropping funnel. 0.30 moles), B 118.0 g (0.50 mol) of alkenyltoluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were stirred and mixed to prepare a solution as a chain transfer agent. It was prepared by adding 6 g of n-dodecyl mercaptan and 24 g of PGMEA, and stirring and mixing.

Then, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C while stirring. Next, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The dropwise addition was carried out for 2 hours while maintaining the temperature at 90 ° C, and after raising the temperature to 110 ° C for 1 hour and maintaining for 3 hours, the nitrogen introduction tube was introduced to start the drum of the oxygen/nitrogen ratio of 5/95 (v/v) mixed gas. bubble. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% relative to the carboxyl group of the acrylic acid used in the present reaction)], 2,2'-methylenebis(4-methyl-) 0.4 g of 6-tert-butylphenol and 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 ° C for 8 hours to obtain a binder resin B1 having an acid value of 70 mg KOH/g as a solid component. The weight average molecular weight of the binder resin B1 measured by GPC was 16,000.

Synthesis Example 2. Adhesive Resin B2

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. The dropping funnel was added dropwise to the flask over 4 hours to 44.5 g of a monomethacrylate containing 70.5 g (0.40 mol) of benzyl methacrylate, 45.0 g (0.50 mol) of methacrylic acid, and an isocyclic skeleton. A solution of 3.6 g of azobisisobutyronitrile was added to a mixture of 136 g of propylene glycol monomethyl ether acetate, and the mixture was further stirred at 100 ° C for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate 30 g [0.2 mol, (40 mol% relative to the carboxyl group of methacrylic acid used in the present reaction)], tris(dimethyl) 0.9 g of aminomethyl)phenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a binder resin B2 having a solid content of 99 mg KOH/g. The weight average molecular weight of the binder resin B2 measured by GPC was 28,000.

Synthesis Example 3. Adhesive Resin B3

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. The liquid funnel was added dropwise to the flask over 7 hours in a solution containing 70.5 g (0.40 mol) of benzyl methacrylate, 45.0 g (0.50 mol) of methacrylic acid, and 2-(2-methyl)adamantyl methacrylate 22.0. A solution obtained by dissolving 3.6 g of azobisisobutyronitrile in a mixture of g (0.10 mol) and propylene glycol monomethyl ether acetate (136 g) was further stirred at 100 ° C for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and glycidyl methacrylate 30 g [0.2 mol, (40 mol% relative to the carboxyl group of methacrylic acid used in the present reaction)], tris(dimethyl) 0.9 g of aminomethyl)phenol and 0.145 g of hydroquinone were placed in a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a binder resin B3 having an acid value of 99 mg KOH/g as a solid component. The weight average molecular weight of the binder resin B3 measured by GPC was 23,000.

Synthesis Example 4: Adhesive Resin B4 containing a monomer represented by Chemical Formula 11

In a four-necked flask equipped with a dropping funnel, a thermometer, a condenser, and a stirrer, methyl-2-(bromomethyl)-acrylate (Aldrich) was placed. 23.3 g, 15.8 g of triethylamine (product of Aldrich Co., Ltd.), and 115.0 g of propylene glycol methyl ether (product of TCI Co., Ltd.), and the inside of the four-necked flask was replaced with nitrogen. Next, after heating the flask to 90 ° C, methyl 2-(hydroxymethyl)-acrylate (product of Aldrich Co., Ltd.) 15.1 g, 2,2'-azobisisobutyronitrile (Wako Corporation) was added dropwise over 1 hour. Product) 3.2 g and a mixed solution of propylene glycol methyl ether (TCI company product) of 110.0 g, and polymerization reaction was carried out for 0.5 hours to produce a pyran-containing polymer.

Next, a mixture of 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 225.0 g of propylene glycol methyl ether, and 3.2 g of 2,2'-azobisisobutyronitrile (product of Wako Co., Ltd.) was gradually added dropwise over 1 hour. The solution was allowed to cool at room temperature after 8 hours of polymerization. After replacing the inside of the four-necked flask with nitrogen, 61.5 parts by weight of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd.), 4.6 g of tetra-n-butylammonium bromide (product of TCI Co., Ltd.), and a pair of nails were added to the flask. 0.15 g of oxyphenol (product of Pure Company) was subjected to a reaction at 80 ° C for 12 hours, and GMA was added to the carboxyl group of the copolymer to obtain a binder resin B4. The weight average molecular weight of the binder resin B4 measured by GPC was 23,000.

Synthesis Example 5: Adhesive Resin B5 containing a monomer represented by Chemical Formula 12

In a four-necked flask equipped with a dropping funnel, a thermometer, a condenser, and a stirrer, 37.5 g of methacrylic acid (product of Kyoei Co., Ltd.) and methyl methacrylate (product of Kyoei Co., Ltd.) 19.0 g, 2, 5 were placed. - 9.1 g of dihydrofuran (product of TCI Co., Ltd.) and 225.0 g of propylene glycol methyl ether (product of TCI Co., Ltd.), and the inside of the four-necked flask was replaced with nitrogen. Next, after heating the flask to 70 ° C, 37.5 g of methacrylic acid, 19.0 g of methyl methacrylate, 9.1 g of 2,5-dihydrofuran, 225.0 g of propylene glycol methyl ether, and 2 were slowly added dropwise over 1 hour. 2'-Azobisisobutyronitrile (product of Wako) 3.2 g of a mixed solution.

After the polymerization for 8 hours, the resultant was allowed to stand at room temperature, and the inside of the four-necked flask was replaced with nitrogen. Then, 61.5 parts by weight of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd.) and tetra-n-butyl were added to the flask. 3.6 g of ammonium bromide (product of TCI Co., Ltd.) and 0.15 g of p-methoxyphenol (product of Pure Company) were reacted at 80 ° C for 12 hours, and GMA was added to the carboxyl group of the copolymer to obtain a binder resin B5. The weight average molecular weight of the binder resin B5 measured by GPC was 17,000.

Examples 1 to 5 and Comparative Examples 1 to 3: Production of color conversion layer

After the solvent is added to the mixer, a dye, a binder resin, a photopolymerizable compound, and a photopolymerization initiator are added thereto, and the mixture is uniformly mixed by stirring to produce a self-luminous photosensitive resin composition. At this time, the composition used was the composition of Table 1 and Table 2 below.

The photosensitive resin composition obtained above was applied onto a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C for 3 minutes to form a film.

Next, ultraviolet rays are irradiated onto the above film. In this case, an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Electric Co., Ltd. was used for the ultraviolet light source, and the light was irradiated at an exposure amount (365 nm) of 40 mJ/cm ² in an air atmosphere, and a special optical filter was not used. .

The film irradiated with the above ultraviolet light was developed in a developing solution of KOH aqueous solution of pH 12.5 using a spray developing device for 60 seconds, and then heated in a heating oven at 220 ° C for 20 minutes to prepare a pattern. The film thickness of the self-luminous color conversion layer pattern produced above was 3.0 μm.

Experimental example: Determination of luminous intensity

In order to confirm whether or not the fluorescence efficiency of the color conversion layer obtained in the above Examples 1 to 5 and Comparative Examples 1 to 3 is increased, the measurement of the light emission with respect to each of the coated substrates is performed using a quantum efficiency measuring device (QE-1000, manufactured by Otsuka Co., Ltd.). PL. At this time, the obtained result is shown in the following Table 3. In this case, the higher the measured luminous intensity means the higher the fluorescence efficiency.

Referring to Table 3 above, it is understood that Examples 1 to 5 have higher luminous intensity values than Comparative Examples 1 to 3, and therefore, the fluorescence efficiency of Examples 1 to 5 is excellent.

Experimental example: heat resistance evaluation

A color filter was produced using the photosensitive resin compositions manufactured in the above Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was applied onto a 2 inch square glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) by a spin coating method, and then placed on a hot plate at 100 ° C. The film was formed at a temperature for 3 minutes. Next, a pattern in which the transmittance was changed stepwise in the range of 1 to 100% and a test photomask having a line/gap pattern of 1 μm to 50 μm were placed on the film, and the interval from the test photomask was set to 100 μm. Ultraviolet light. At this time, the ultraviolet light source was irradiated with a 1 kW high-pressure mercury lamp containing all g, h, and i rays at an illuminance of 100 mJ/cm ² , and a special optical filter was not used. The film irradiated with the above ultraviolet rays was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes for development. The glass plate coated with the above film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C for 25 minutes to produce a color filter. The film thickness of the above-described color filter was 2.0 μm.

Heat resistance

Regarding the heat resistance, the color change value (ΔEab) after heating at 230 ° C for 120 minutes was measured and evaluated. ΔEab is a value required by the following chroma formula based on the color system of the CIE1976 (L*, a*, b*) space. (The Japanese Color Society edited a new color science manual (Showa 60), p. 266).

△E*ab={(△L) ² +(△a) ² +(△b) ² } ^1/2

[Heat resistance evaluation standard]

○: △E*ab value: 3 or less

△: △E*ab value: 3~10 or less

X: △ E * ab value: more than 10

Experimental example: Evaluation of light resistance

A color filter was produced using the photosensitive resin compositions manufactured in the above Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was applied onto a 2 inch square glass substrate ("EAGLE XG" manufactured by Corning Co., Ltd.) by a spin coating method, and then placed on a hot plate at 100 ° C. The film was formed at a temperature for 3 minutes. Next, a pattern in which the transmittance was changed stepwise in the range of 1 to 100% and a test photomask having a line/gap pattern of 1 μm to 50 μm were placed on the film, and the interval from the test photomask was set to 100 μm. Ultraviolet light. At this time, the ultraviolet light source was irradiated with a 1 kW high-pressure mercury lamp containing all g, h, and i rays at an illuminance of 100 mJ/cm ² , and a special optical filter was not used. The film irradiated with the above ultraviolet rays was immersed in a developing solution of KOH aqueous solution having a pH of 10.5 for 2 minutes for development. The glass plate coated with the above film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C for 25 minutes to produce a color filter. The film thickness of the above-described color filter was 2.0 μm.

Lightfastness

For the light resistance, the chromaticity and transmittance of the substrate produced in the above experimental example were measured by a colorimeter (manufactured by Olympus Co., Ltd., OSP-200), and the substrate having the color coordinates was measured in the light resistance equipment (ATLAS). CPS+ equipment) After the irradiation for 200 hr, the chromaticity and the transmittance were measured again using a colorimeter (manufactured by Olympus, OSP-200).

ΔEab is a value required by the following chroma formula based on the color system of the CIE1976 (L*, a*, b*) space. (The Japanese Color Society edited a new color science manual (Showa 60), p. 266).

△E*ab={(△L) ² +(△a) ² +(△b) ² } ^1/2

[Light resistance evaluation criteria]

○: △E*ab value: 3 or less

△: △E*ab value: 3~10 or less

X: △ E * ab value: more than 10

Experimental example: development speed

The colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were each applied onto a glass substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C for 3 minutes to form a film. Thereafter, ultraviolet rays of 50 mJ/cm ² were irradiated through the entire surface exposure without a photomask, and then the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK6M; manufactured by Veeco Co., Ltd.). After the substrate having been subjected to the measurement of the thickness was immersed in the KOH aqueous solution development solution having a pH of 10.5 for 80 seconds and developed, the presence or absence of the self-luminous photosensitive resin composition was confirmed in the portion of the non-exposed portion.

[Development speed evaluation standard]

At the time of development, the time taken for the non-exposed portion to completely dissolve in the developer was measured and shown. The case of undeveloped is expressed as "X".

Referring to the above Table 3, it is understood that Examples 1 to 5 produced by using the binder resin containing a pyran or furan structure according to the present invention are excellent in heat resistance and light resistance, and the development speed is also fast. On the other hand, in the case of Comparative Examples 1 to 3, it was confirmed that the development speed was also slow, and neither heat resistance nor light resistance was excellent.

The embodiments of the present invention have been described above with reference to the drawings, but the present invention is not limited to the above-described embodiments, and can be modified into various ways that are different from each other, but a technique having ordinary knowledge in the technical field to which the present invention pertains. It should be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit and scope of the invention. The above-described embodiments are therefore to be considered in all respects as illustrative and

1‧‧‧Substrate

3‧‧‧Color conversion layer

5‧‧‧Color filters

Claims (8)

A self-luminous photosensitive resin composition which is a composition for forming a color conversion layer, comprising a fluorescent dye, a photopolymerizable compound, a photopolymerization initiator, a binder resin, and a solvent, wherein the photopolymerization initiator is An oxime ester photopolymerization initiator. The self-luminous photosensitive resin composition of claim 1, wherein the oxime ester-based photopolymerization initiator is one or more selected from the group consisting of the compounds represented by the following Chemical Formulas 1 to 9: In the above Chemical Formula 1, R ₁ is -R ₄ -R ₅ , in which case, R ₄ is an alkylene group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 3 to 8 carbon atoms or a cycloalkyl group, and R ₂ Is an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ₃ is a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms substituted by an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or a second group. Phenyl sulfide group, Chemical Formula 2, R ₆ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, R ₇ is -R ⁸ -R ^9, at this time, R ₈ is an alkylene group having a carbon number of 1 to 4; R ₉ is An alkyl group having a carbon number of 3 to 8 or a cycloalkyl group, In the chemical formula 3, X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁₀ to R ₁₂ each independently represent -R, -OR, -COR, -SR, -CONRR', or -CN. In this case, R and R' represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 5- to 7-membered heterocyclic group. One or more substitutions selected from the group consisting of a halogen atom and a 5- to 7-membered heterocyclic group, wherein the alkylene group of the alkyl group and the aralkyl group may be an unsaturated bond, an ether bond, a thioether bond, or an ester. The bond is interrupted, and R and R' may form a ring together, and R ₁₃ to R ₁₆ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and Y ¹ to Y ³ are each independently S. O, or Se, m represents an integer from 0 to 4, p represents an integer from 0 to 5, and q represents 0 or 1, In the chemical formula 4, R ₁₇ to R ₂₆ are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 7 An arylalkyl group of ~40, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. In the above Chemical Formula 5, R ₂₇ is (II), n is an integer of 1 to 4, m is an integer of 1 to 6, R ₂₈ is an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ₂₉ is , In the chemical formula 6, X represents a halogen atom or an alkyl group, and R ₃₀ , R ₃₁ and R ₃₂ each independently represent R, OR, COR, SR, CONRR', or CN, and R and R' represent an alkyl group or an aryl group. Or an aralkyl group or a heterocyclic group, which may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, wherein the alkylene group of the alkyl group and the aralkyl group may be unsaturated. The ether bond, the thioether bond, and the ester bond are interrupted. Further, R and R' may form a ring together, Y ¹ represents an oxygen atom, a sulfur atom, or a selenium atom, A represents a heterocyclic group, and m represents an integer of 0-4. p represents an integer from 0 to 5, and q represents 0 or 1. In the above Chemical Formula 7, R ₃₃ , R ₃₄ , R ₃₅ , X, Y ¹ , m, p and q are the same as the above Chemical Formula 6, and R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and Y ² and Y ³ each independently represent an oxygen atom, a sulfur atom, or a selenium atom, In the chemical formula 8, R ₄₀ , R ₄₁ , R ₄₂ , X, Y ¹ , m, p and q are the same as the above Chemical Formula 6, X' represents a halogen atom or an alkyl group, and r represents an integer of 0-4. In Chemical Formula 9, R ₄₃ , R ₄₄ , R ₄₅ , X, Y ¹ , m, p and q are the same as those in Chemical Formula 6, X′′ represents a halogen atom or an alkyl group, and s represents an integer of 0-4. The self-luminous photosensitive resin composition of claim 1, wherein the binder resin contains one or more repeating units of the following chemical formula 10, In the chemical formula 10, R ₄₆ , R ₄₇ , R ₄₈ and R ₄₉ are each independently hydrogen, a halogen group, a C1 to C10 alkyl group, a C5 to C10 cycloalkyl group, or a C6 to C20 aryl group. The aryl group may be substituted with N, O, or S, and n is 0 or 1. The self-luminous photosensitive resin composition of claim 3, wherein the binder resin contains a repeating unit in which all n is 1 and a repeating unit in which n is 0. The self-luminous photosensitive resin composition of claim 1, wherein the photopolymerization initiator further contains an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone One or more of the groups consisting of the compounds. The self-luminous photosensitive resin composition according to claim 1, wherein the self-luminous photosensitive resin composition further contains one selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group. The above photopolymerization initiation adjuvant. The self-luminous photosensitive resin composition of claim 1, which comprises 0.1 to 30% by weight of a fluorescent dye and 5 to 60% by weight of a photopolymerizable compound, based on the total weight of the solid content of the self-luminous photosensitive resin composition. % and 60% by weight of the binder resin, and 0.1 to 40 parts by weight of the photopolymerization initiator based on 100 parts by weight of the total of the content of the photopolymerizable compound and the binder resin, based on the solid content . A display device comprising a color conversion layer produced by using the self-luminous photosensitive resin composition according to any one of claims 1 to 7 on the upper portion of the substrate.