JP6741427B2 - Self-luminous photosensitive resin composition, display device including color conversion layer produced therefrom - Google Patents

Description

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

Recently, the display industry has rapidly changed from CRT (cathode-ray tube) to PDP (plasma display panel), OLED (organic light-emittering diode), LCD (liquid-crystal display), etc. Has been achieved. Among them, the LCD is widely used in the image display device used in almost all industries, and its application range is continuously expanding.

In the LCD, the white light generated from the backlight unit has its transmittance adjusted while passing through the liquid crystal cell, and the three primary colors that are emitted through the red (Red), green (Blue), and blue (Blue) color filters are mixed. Is achieved to achieve full color.

A CCFL (Cold Cathode Fluorescent Lamp) is used as a light source of the backlight unit. In this case, the backlight unit must constantly apply power to the CCFL, which causes a problem of power consumption. Further, it is pointed out that the color reproduction rate is about 70% of that of the existing CRT and the problem of environmental pollution due to addition of mercury.

As a substitute for solving the above problems, a backlight unit using an LED (Light Emitting Diode) has been actively researched so far. When the LED is used as the backlight unit, it is more than 100% of the NTSC (National Television System Committee) color reproduction range specification, and it is possible to provide a more vivid image quality to the consumer.

Therefore, in the same type of industry, in order to improve the efficiency of the backlight light source, a method is proposed in which the materials and structures of the color filter and the LCD panel are changed.

The color filter forms pixels of each color by a patterning process after applying a dispersion composition containing a pigment or a dye, but such a pigment and a dye cause a problem of lowering the transmission efficiency of a backlight light source. The decrease in the transmission efficiency results in a decrease in the color reproducibility of the display device, and eventually 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, where the thickness of the color filter is increased, or a color conversion layer (or a light conversion layer) is laminated or close to it. A method of introducing it has been proposed.

FIG. 1 is a schematic view showing the role of the color conversion layer in the display device. As shown in FIG. 1, the light source generated from the backlight 1 directly changes the light efficiency through the color conversion layer 3 and the color filter 5. Can be increased to

Although existing dyes and pigments are used for the composition of the color conversion layer, it is difficult to expect improvement in light efficiency with such dyes and pigments alone, and there is a problem that the brightness is rather lowered. Therefore, it has been proposed to use a fluorescent substance as the substance of the color conversion layer 3.

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

A number of patents have been filed for a color conversion layer having a fluorescent material, and in the patent document 1, the patent document 1 is disposed between a backlight unit and a substrate or is disposed above a shutter unit, and has a wavelength of blue or ultraviolet. Reference is made to a display device having a light conversion part having at least one fluorescent substance for converting incident light of a band into light of a predetermined wavelength band.

Patent Document 2 proposes a liquid crystal display device including a backlight unit capable of improving light efficiency. At this time, in order to improve light efficiency, a phosphor, a quantum dot (Quantum Dot), a white scatterer, and It presents the introduction of color conversion materials such as electroluminescent and photoluminescent materials.

Patent Document 3 presents a method of introducing a color conversion layer made of a green light emitting phosphor in order to improve the brightness of a white light emitting diode (LED).

These patents aim to improve the quality of the display device by introducing a color conversion layer containing a phosphor or the like, but at this time, the method for forming the color conversion layer is not directly mentioned or even if it is mentioned. , A method of wet coating after simple dispersion in a solvent is presented.

As shown in FIG. 1, the color conversion layer may be formed in a pattern corresponding to the red R and green G pixel portions of the color filter. At this time, the size of the color conversion layer may be several hundred microns. Since the above-mentioned phosphor is in a state of being dispersed without being dissolved in a solvent, it is difficult to realize a fine pattern and it is not easy to adjust physical properties such as thickness.

Such difficulty can be eliminated by enabling the realization of a fine pattern by a photolithography method using a photosensitive resin composition.

In the case of a general photosensitive resin composition, a photoinitiator is used for polymerization, but radicals generated from the photoinitiator not only lower the fluorescence efficiency of the phosphor, but also perform a photolithography process. In the post-baking process performed inside, a new problem such as yellowing of the color conversion layer due to the photoinitiator was brought about.

Korean Published Patent No. 2012-0048218 Korean Published Patent No. 2013-0083807 JP, 2013-077825, A

The present invention is to solve the above problems, by using a specific photopolymerization initiator in a specific content, shows excellent color conversion characteristics and high fluorescence efficiency, a specific binder resin It is to provide a self-luminous photosensitive resin composition capable of enhancing the developing rate and the adhesiveness by including the above.

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

In order to achieve the above object, the present invention is a composition for forming a color conversion layer, a fluorescent dye, an antioxidant, a binder resin, a photopolymerizable compound, an oxime ester-based photopolymerization initiator, And a solvent.

The present invention also features a display device including a color conversion layer manufactured from the self-luminous photosensitive resin composition.

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

The display device incorporating the color conversion layer manufactured from the self-luminous photosensitive resin composition maintains high brightness, ensures excellent color conversion characteristics and high light efficiency, and provides high-quality vivid image quality. Can be realized.

It is a schematic diagram showing the role of the color conversion layer in the display device.

The present invention provides a self-luminous photosensitive resin composition that can be used in the color conversion layer of a display device.

The color conversion layer is located adjacent to the color filter (see FIG. 1) to improve the reduced light efficiency caused by the use of the color filter, and corresponds to the red R, green G pattern of the color filter. Consists of a fine pattern.

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

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

In particular, in the present invention, a photosensitive resin composition containing a fluorescent dye and a specific photopolymerization initiator as essential components in the composition of the color conversion layer is presented, and the fluorescent efficiency due to spontaneous emission of the fluorescent dye is the overall light efficiency. In the photosensitive resin composition, a fine pattern can be formed, and with a high-sensitivity photopolymerization initiator, the effect of preventing a decrease in fluorescence efficiency is secured.

More specifically, the oxime ester-based initiator having a diphenyl sulfide structure or the oxime ester-based initiator having a carbazole structure according to the present invention has high sensitivity and can achieve a sufficient curing rate with a small amount, so that the fluorescence efficiency is high. It is possible to suppress the decrease.

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

Hereinafter, each composition will be described.

The fluorescent dye contained in the self-luminous photosensitive resin composition of the present invention is a solvent (solvent), an acid (acid), a basic (color) in a color index (Color Index) [The Society of Dyers [0119] and Colorists publication]. Examples thereof include dyes classified as Basic, Reactive, Direct, Disperse, and Vat. More specifically, dyes having the following color intex (C.I.) numbers are mentioned, but the dyes are not limited to these.
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. Disperse 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. Solvent Green 1, 5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Common fluorescent dyes include coumarin dyes such as 3-(2-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6), 3-(2-benzimidazolyl)-7-diethylaminocoumarin (coumarin 7) and coumarin 135. Including. Further, naphthalimide dyes such as Solvent Yellow 43 and Solvent Yellow 44 may be used. In addition, various low molecular light emitting materials and various polymer light emitting materials are also applicable.

Quinacridone derivatives such as diethylquinacridone (DEQ); 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM-1, (I)), DCM-2(II), and Cyanine dye such as DCJTB (III); 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene (IV), Lumogen F red, Nile red ( V) etc. are included. Alternatively, 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-diethylaminocoumarin (coumarin 6). , 3-(2-benzimidazolyl)-7-diethylaminocoumarin (coumarin 7), coumarin-based pigments such as coumarin 135; low-molecular-weight pigments such as Solvent Yellow 43 and solvent yellow 44. Contains organic fluorescent dyes. Alternatively, a polymeric fluorescent material typified by polyphenylene, polyarylene, or polyfluorene may be used as the color conversion dye.

In some cases, a mixture of two or more 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 such as when converting blue light to red light. The dye mixture may be a mixture of the above-mentioned dyes. Further, a mixture of the above-mentioned dye and the following dye may be used. Quinacridone derivatives such as diethyl quinacridone (DEQ); 4-dicyanomethylene-2-methyl, (p-dimethylaminostyryl)-4H-pyran (DCM-1, (I)), DCM- 2(II), and cyanine dyes such as DCJTB(III); 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza (Diaza)-s-indacene (IV); Lumogen F red, Lumogen F orange, Lumogen F yellow, Nile Red (V), Rhodamine. B, xanthene-based dyes such as rhodamine 6G; and pyridine-based dyes such as pyridine 1 are preferable.

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 included in the above range, it does not cause a problem in the pattern formation of the color conversion layer, and a sufficient improvement in light efficiency can be expected.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound which is polymerizable by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer or a bifunctional monomer. , And other polyfunctional monomers. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone. 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)acrylate, bisphenol. Examples thereof include bis(acryloyloxyethyl) ether of A and 3-methylpentanediol di(meth)acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol. Hexa(meth)acrylate and the like can be mentioned. Among these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound is used in the range 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 included 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 photopolymerization initiator may be one or more selected from the group consisting of compounds represented by the following chemical formulas 1 to 9.

(In the above chemical formula 1,
R ₁ is

Wherein R ₄ is an alkylene group having 1 to ₄ carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,
R ₂ is an alkyl group having 1 to 8 carbon atoms or a phenyl group,
R ₃ is a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or a 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,
R ₇ is

Wherein R ₈ is an alkylene group having 1 to 4 carbon atoms; R ₉ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms. )

(In the above chemical formula 3,
X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms,
R ₁₀ to R ₁₂ are each, independently, -R, -OR, -COR, -SR , -CONRR ', or represents -CN, this time, the R and R' is 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, which is selected from the group consisting of a halogen atom and a 5 to 7-membered heterocyclic group. It may be substituted with one or more kinds, and among these, the alkylene portion of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R′ are They may form a ring together,
R _{13 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms,
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,
q represents 0 or 1. )

Preferably, in the above Chemical Formula 1, the alkyl group represented by R and R′ is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl. , Heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, proproxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl. , Proproxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazol-2′-yl)ethenyl, etc., among which the number of carbon atoms is included. 1-8 alkyl groups are preferred.

Examples of the aryl group represented by R and R′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like, and among them, having 6 to 12 carbon atoms. Aryl groups are preferred. Examples of the aralkyl group represented by R and R′ include aralkyl having 7 to 13 carbon atoms such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and phenylethenyl. A group is preferably mentioned. As the heterocyclic group represented by R and R′, for example, a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl and thiophenyl is preferably exemplified. Further, as the ring which R and R′ can form together, a ring having 5 to 7 carbon atoms such as piperidine ring and morpholine ring is preferably exemplified. Further, R and R′ are substituted with a halogen element such as fluorine, chlorine, bromine, iodine, or pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl( Pyrazolidyl), thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, and piperidyl, such as isoperazolyl-5, piperidyl, and piperidyl. It may be substituted.

Examples of the halogen atom represented by X include fluorine, chlorine, bromine and iodine. The alkyl group represented by X is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl which is substituted with a halogen atom or is not substituted. , Octyl, isooctyl, 2-ethylhexyl and tert-octyl.

Examples of the halogen atom represented by R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ in the chemical formula 3 include fluorine, chlorine, bromine and iodine.

Further, in the above chemical formula 3, the alkyl group represented by R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl substituted or not with a halogen atom, Examples include tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, and tert-octyl.

The oxime ester compound of the present invention represented by the chemical formula 3 may be preferably the following compound.

Examples of commercially available products having the structure of Chemical Formula 3 include N-1919 (ADEKA Corporation).

(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. It is an arylalkyl group having 7 to 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.)

R _{17 to} R ₂₆ are specifically hydrogen, bromo, chloro, iodo, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group. , N-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n -Propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n-propyl group, hydroxy n-butyl group, hydroxy i-butyl group Group, hydroxy n-pentyl group, hydroxy i-pentyl group, hydroxy n-hexyl group, hydroxy i-hexyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, hydroxymethoxypropyl group, hydroxymethoxybutyl group, hydroxyethoxymethyl group It may be a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group, or a hydroxyethoxyhexyl group.

Preferably, R ₁₇ is hydrogen, methyl group, ethyl group, propyl group, or butyl group; R ₁₈ is methyl group, ethyl group, or propyl group; R ₁₉ is methyl group, ethyl group, propyl group Or a butyl group; R _{20 to} R ₂₆ may be hydrogen.

Typical examples of the fluorene-based initiator used in the present invention include the following compounds, but the fluorene-based initiators are not limited to the following examples, and any of those known in the art as those satisfying the above conditions can be used. ..

(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,
R ₂₉ is

Is. )

(In the above chemical formula 6,
X represents a halogen atom or an alkyl group,
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 aryl group, an aralkyl group or a heterocyclic group. , These may be substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group, and among these, the alkylene portion of the alkyl group and the aralkyl group is an unsaturated bond, an ether bond, a thioether bond, It may be interrupted by an ester bond, and R and R'may together form a ring. Y ¹ represents an oxygen atom, a sulfur atom, or a selenium atom, A represents a heterocyclic group, m represents an integer of 0 to 4, p represents an integer of 0 to 5, and q represents 0 or 1. .. )

(In the chemical formula 7,
R ₃₃ , R ₃₄ , R ₃₅ , X, Y ¹ , m, p and q are the same as those in the chemical formula 6,
R ₃₆ , R ₃₇ , R _38, and R ₃₉ each independently represent a hydrogen atom, a halogen atom, or an alkyl group,
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 those in 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 those in Chemical Formula 6,
X" represents a halogen atom or an alkyl group, and s represents an integer of 0-4."

Further, a photopolymerization initiator other than the above may be additionally used within a range not impairing the effects of the present invention. Typically, it is preferable to use one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy). Phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl 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 can be mentioned.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxide). (Oxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and 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-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4 -Methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4- Diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5- Examples include triazine.

Specific examples of the biimidazole-based 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'-tetra(alkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5' -Tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group. Of these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4', 5,5'-Tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferably used.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

The self-luminous photosensitive resin composition according to the present invention may further include a photopolymerization initiation auxiliary agent. The self-luminous photosensitive resin composition according to the present invention can further improve sensitivity and improve productivity by additionally containing a photopolymerization initiation auxiliary agent.

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

As the amine compound, it is preferable to use an aromatic amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethyl. Ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (Common name: Michler's ketone), 4,4′-bis(diethylamino)benzophenone and the like can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid. , Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl). -1,3,5-Triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol Tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned.

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

When the photopolymerization initiator is included in the above range, the self-luminous photosensitive resin composition has high sensitivity and exposure time is shortened, so that productivity is improved and high resolution can be maintained, which is preferable. .. In addition, the strength of the pixel portion formed using the composition of the above conditions and the smoothness on the surface of the pixel portion are improved.

When the photopolymerization initiation auxiliary agent is further included, the photopolymerization initiation auxiliary agent is 0.1 to 100 parts by weight based on the total solid content of the photopolymerizable compound and the binder resin. ˜40 parts by weight, preferably 1 to 30 parts by weight. When the amount of the photopolymerization initiation auxiliary agent used is in the range of 0.1 to 40 parts by weight, the sensitivity of the self-luminous photosensitive resin composition is further increased, and a color filter formed using the composition. Providing the effect of improving productivity.

The binder resin contained in the self-luminous photosensitive resin composition of the present invention usually has reactivity and alkali solubility under the action of light or heat, and acts as a dispersion medium for the coloring material. The binder resin contained in the self-luminous photosensitive resin composition of the present invention acts as a binder resin for a fluorescent dye, and is a bond soluble in the alkaline developer used in the developing step for manufacturing a color filter. Any agent resin 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, additionally, a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with this monomer may be mentioned.

(In the above 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, wherein the aryl group can be substituted with N, O, or S,
n is 0 or 1. )

Halogen referred to in the present invention is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The alkyl group referred to in the present invention includes straight chain or branched chain, and as one example, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, n- Hexyl, n-octyl, n-decyl and the like are included.

Cycloalkyl groups referred to in this invention include cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbornyl, norbornenyl and the like.

Aryl groups referred to in this invention include phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.

At this time, the binder resin may include a repeating unit having n=1 and a repeating unit having n=0, and the repeating unit having n=1 is obtained by polymerizing a monomer represented by the following Chemical Formula 11. , N is a repeating unit obtained by polymerizing a monomer represented by the following chemical formula 12, and will be described in detail below.

By including the binder resin of the chemical formula 10 having the pyran or furan structure as described above, the developing speed is increased, which is advantageous in terms of the process.

In the 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, more preferably 25 to 50% by weight based on the total weight of the binder resin. It is 40% by weight. Within the above range, there are advantages of adhesion and transparency.

At this time, the chemical formula 10 can be represented by polymerizing one or more monomers of the chemical formulas 11 and 12.

(In the above 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, wherein the aryl group can be substituted with N, O, or S. )

As an example, according to an exemplary embodiment of the present invention, a material satisfying the structure of Chemical Formula 11 may be directly manufactured or a commercially available product may be purchased and used as methyl-2-(bromomethyl)-acrylate (product of Aldrich Co.). It is obtained by polymerization of triethylamine (product of Aldrich) and methyl-2-(hydroxymethyl)-acrylate (product of Aldrich). As the solvent used for the polymerization, propylene glycol methyl ether (manufactured by TCI) and 2,2'-azobisisobutyronitrile (manufactured by Wako) can be used.

(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, wherein the aryl group can be substituted with N, O, or S. )

The copolymer including the repeating unit of Chemical Formula 12 may be substituted or unsubstituted dihydrofuran or may be polymerized by the method of Chemical Formula 11, and such a material may be directly manufactured or commercially available. The product can be purchased and used.

Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and other unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. Examples thereof include carboxylic acid.

Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. 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 its mono(2-methacryloyloxyalkyl)ester, for example, mono(2-acryloyloxyethyl)succinate, mono(2-methacryloyloxyethyl)succinate, Examples thereof include mono(2-acryloyloxyethyl) phthalate and mono(2-methacryloyloxyethyl) phthalate. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

These carboxyl group-containing monomers can be used alone or in admixture of two or more. Examples of the other monomer copolymerizable with the 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-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate , N-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylic acid , Isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy Unsaturated carboxylic acid esters such as -3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2 -Aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; vinyl methyl ether Unsaturated vinyl ethers such as vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2- Unsaturated amides such as hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; 1,3-butadiene, isoprene, chloroprene, etc. Polymers of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, monoacryloyl group or monomethacryloyl group And giant monomers having

These monomers can be used alone or in admixture of two or more. Particularly, as the other monomer copolymerizable with the 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. It is preferred because the body tends to lower the relative dielectric constant value.

These monomers can be used alone or in admixture of two or more. When the binder resin is a copolymer with a carboxyl group-containing monomer and another monomer copolymerizable with this monomer, the content of structural units derived from the carboxyl group-containing monomer The ratio is 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight, based on the total content of the constituent units constituting the copolymer. is there. 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 standard, the solubility in a developing solution is good, and a pattern is accurately formed during development. Therefore, it is preferable. Further, the content of the other monomer copolymerizable with the carboxyl group-containing monomer is 10 to 50% by weight based on the total content of the constituent units constituting the copolymer. , Preferably 15 to 40% by weight, more preferably 25 to 40% by weight.

The binder resin is used in the range of 1 to 60% by weight, preferably 5 to 50% by weight, based on the total weight of solids in the self-luminous photosensitive resin composition of the present invention. It is preferable that the binder resin is contained in the range of 1 to 60% by weight based on the above-mentioned criteria because the solubility is good and the pattern formation is excellent.

The binder resin of the present invention preferably has an acid value of 20 to 200 (KOHmg/g). When the acid value is within the above range, the solubility in the developing solution is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion remains during development and the residual film rate (film). It is preferable because it improves the remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and usually, it is determined by titrating with an aqueous potassium hydroxide solution. Desired. Further, the polystyrene-converted weight average molecular weight (hereinafter, simply 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 binder resins are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is excellent, and the resolution is improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the binder resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 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 other ethylene glycol monoalkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether. Ethylene glycol alkyl ether acetates such as diethylene glycol dialkyl ethers, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl Alkylene glycol alkyl ether acetates such as acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, ethanol, propanol, butanol, hexanol Alcohols such as cyclohexanol, ethylene glycol, and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, cyclic esters such as γ-butyrolactone, and the like. Among the above solvents, organic solvents having a boiling point of 100° C. to 200° C. are preferable in terms of coating properties and drying properties, and more preferable are alkylene glycol alkyl ether acetates, ketones, and 3-ethoxypropionic acid. Examples of the esters include ethyl and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. Is mentioned. These solvents may be used alone or in admixture 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, 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, the coatability becomes good when coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), and an inkjet. ..

In the self-luminous photosensitive resin composition of the present invention, if necessary, additives such as a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent. It is also possible to use together. Specific examples of the filler include glass, silica, alumina and the like. Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane. And so on. As the pigment dispersant, a commercially available surfactant is used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-, anionic-, nonionic-, and amphoteric-based surfactants. These can be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Yes, in addition, as product names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Megafac (MEGAFAC) (Manufactured by Dainippon Ink and Chemicals, Inc.), Florad (manufactured by Sumitomo 3M Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (SOLLSPERSE) ) (Manufactured by Zeneca Corp.), EFKA (manufactured by EFKA Chemicals), PB821 (manufactured by Ajinomoto Co., Inc.) and the like. As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl) )-3-Aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri Examples thereof include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. Specific examples of the antioxidant include 2,2′-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-<81>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 aggregation preventing agent include sodium polyacrylate.

The self-luminous photosensitive resin composition of the present invention can be produced, for example, by the following method. The dye is mixed with the solvent in advance and dissolved. At this time, a pigment dispersant is used if necessary, and a part or all of the binder resin may be mixed. In the obtained dispersion (hereinafter, also referred to as millbase), the remainder of the binder resin, the photopolymerizable compound, and the photopolymerization initiator, other components used as necessary, and an additional solvent as necessary. Is further added so as to have a predetermined concentration to obtain the desired self-luminous photosensitive resin composition.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is merely exemplary, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined in the claims, and includes the meaning equivalent to the record of the claims and all modifications within the scope. Moreover, "%" and "part" which show content below are mass references|standards unless there is particular mention.

Synthesis example 1. Binder resin B1
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube was prepared, while as a monomer dropping funnel, 74.8 g (0.20 mol) of benzyl maleimide and 43.2 g (0 .30 mol), 118.0 g (0.50 mol) of vinyltoluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) are added after stirring and mixing, A chain transfer agent dropping tank was prepared by mixing 6 g of n-dodecanethiol and 24 g of PGMEA and stirring and mixing them.

Then, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then 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 dropping was continued for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 3 hours, and then a gas inlet tube was introduced to introduce oxygen/nitrogen=5/95 (v/v). Bubbling of the mixed gas was started. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t) -Butylphenol) (0.4 g) and triethylamine (0.8 g) were charged into the flask and the reaction was continued at 110°C for 8 hours to obtain a binder resin B1 having an acid value of solid content of 70 mgKOH/g. The weight average molecular weight of the binder resin B1 measured by GPC was 16,000.

Synthesis example 2. Binder resin B2
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100°C. , Benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 45.0 g (0.50 mol), isocyclic skeleton monomethacrylate 44.5 g (0.10 mol), and propylene glycol monomethyl ether acetate 136 g. A solution in which 3.6 g of azobisisobutyronitrile was added to the containing mixture was added dropwise to the flask through the dropping funnel over 2 hours, and the stirring was further continued at 100° C. for 5 hours.

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

Synthesis example 3. Binder resin B3
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube, and after changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100° C., Benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 45.0 g (0.50 mol), 2-(2-methyl)adamantyl methacrylate 22.0 g (0.10 mol), and propylene glycol monomethyl ether acetate 136 g. A solution obtained by adding 3.6 g of azobisisobutyronitrile to the mixture containing was added dropwise to the flask through the dropping funnel over 2 hours, and stirring was further continued at 100° C. for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and 30 g of glycidyl methacrylate [0.2 mol, (40 mol% relative to the carboxyl group of methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol. , And hydroquinone (0.145 g) were charged into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a binder resin B3 having an acid value of solid content of 99 mgKOH/g. The weight average molecular weight of the binder resin B3 measured by GPC was 23,000.

Synthesis Example 4: Binder resin B4 containing the monomer represented by the chemical formula 11
In a four-necked flask equipped with a dropping funnel, a thermometer, a cooling tube, and a stirrer, 23.3 g of methyl-2-(bromomethyl)-acrylate (product of Aldrich), 15.8 g of triethylamine (product of Aldrich), and propylene glycol. 115.0 g of methyl ether (product of TCI Co., Ltd.) was put therein, and the inside of the four-necked flask was replaced with nitrogen. Next, after heating the flask to 90° C., 15.2 g of methyl-2-(hydroxymethyl)-acrylate (product of Aldrich) and 3.2 g of 2,2′-azobisisobutyronitrile (product of Wako). , And propylene glycol methyl ether (manufactured by TCI) 110.0 g were added dropwise over 1 hour, and the polymerization reaction was allowed to proceed for 0.5 hour to produce a pyran-containing polymer.

Next, a mixed solution 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) was taken for 1 hour. The mixture was gradually added dropwise, polymerization was carried out for 8 hours, and the mixture was allowed to cool at room temperature. After substituting the inside of the four-necked flask with nitrogen, 61.5 parts by weight of glycidyl methacrylate (product of Mitsubishi Rayon Co., Ltd.), 3.6 g of tetra-n-butylammonium bromide (product of TCI Co.) and metquinone (product of genuine company) were placed in the flask. ) 0.15 g was added and the reaction was carried out at 80° C. for 12 hours to add GMA 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: Binder Resin B5 Containing Monomer Represented by Chemical Formula 12
In a four-necked flask equipped with a dropping funnel, a thermometer, a cooling tube, and a stirrer, methacrylic acid (Kyoeisha product) 37.5 g, methyl methacrylate (Kyoeisha product) 19.0 g, and 2,5-dihydrofuran (TCI product) ) 9.1 g and propylene glycol methyl ether (manufactured by TCI Co., Ltd.) 225.0 g were put, 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 2,2′-azobis. A mixed solution of 3.2 g of isobutyronitrile (manufactured by Wako) was gradually added dropwise over 1 hour.

After polymerization for 8 hours, the resulting product was allowed to cool at room temperature, the inside of the four-necked flask was replaced with nitrogen, and then 61.5 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), tetra-n-butylammonium bromide ( 3.6 g of TCI product) and 0.15 g of metoquinone (pure product) were added, and the reaction was carried out at 80° C. for 12 hours to add GMA to the carboxyl group of the copolymer to obtain binder resin B5. Got The weight average molecular weight of the binder resin B5 measured by GPC was 17,000.

Examples 1-5 and Comparative Examples 1-3: Production of color conversion layer After adding a solvent to a mixer, a dye, a binder resin, a photopolymerizable compound, and a photopolymerization initiator were added thereto. Then, the mixture was uniformly mixed by stirring to produce a self-luminous photosensitive resin composition. At this time, the composition is as shown in Tables 1 and 2 below.

The obtained photosensitive resin composition was applied on a glass substrate by a spin coating method, placed on a heating plate and kept 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, as an ultraviolet light source, an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Inc. was used to irradiate light with an exposure amount (365 nm) of 40 mJ/cm ^{2 in} the air atmosphere to obtain a special light. No optical filter was used.

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

Experimental Example: Measurement of luminescence intensity In order to confirm whether or not the fluorescence efficiency of the color conversion layers obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is increased, an adoption efficiency measuring instrument ( QE-1000, manufactured by Otsuka Co., Ltd. was used to measure the emission PL of each coated substrate. The results obtained at this time are shown in Table 3 below, in which the higher the emission intensity measured, the higher the fluorescence efficiency.

Referring to Table 3, Examples 1 to 5 have higher emission intensity values than Comparative Examples 1 to 3, and thus Examples 1 to 5 are superior in fluorescence efficiency.

Experimental Example: Evaluation of heat resistance A color filter was manufactured using the photosensitive resin compositions manufactured in Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was applied on a 2-inch square glass substrate (manufactured by Corning Incorporated, "EAGLE XG") by spin coating, and then placed on a heating plate at 100°C. The temperature was maintained for 3 minutes to form a thin film. Next, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line/space pattern of 1 μm to 50 μm is placed on the thin film, and the distance from the test photomask is set. It was made 100 μm and irradiated with ultraviolet rays. At this time, the ultraviolet light source was a high-pressure mercury lamp of 1 KW containing all g, h, and i rays, and was irradiated with an illuminance of 100 mJ/cm ^{2, and} no special optical filter was used. The ultraviolet-irradiated thin film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes for development. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to manufacture a color filter. The manufactured color filter had a film thickness of 2.0 μm.

Heat resistance The heat resistance was evaluated by measuring a color change value (ΔEab) after heating at 230° C. for 120 minutes. ΔEab is a value required by the following saturation formula based on the color system of the CIE1976 (L*, a*, b*) space. (Handbook of Color Science, New Edition, edited by Japan Color Society (1985), p. 266).
ΔE*ab={(ΔL) ² +(Δa) ² +(Δb) ² } ^1/2
[Heat resistance evaluation criteria]
◯: ΔE*ab value: 3 or less Δ: ΔE*ab value: 3 to 10 or less ×: ΔE*ab value: 10 or more

Experimental Example: Evaluation of light resistance A color filter was manufactured using the photosensitive resin compositions manufactured in Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was applied on a 2-inch square glass substrate (manufactured by Corning Incorporated, "EAGLE XG") by spin coating, and then placed on a heating plate at 100°C. The temperature was maintained for 3 minutes to form a thin film. Next, a test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line/space pattern of 1 μm to 50 μm is placed on the thin film, and the distance from the test photomask is set. It was made 100 μm and irradiated with ultraviolet rays. At this time, the ultraviolet light source was a high-pressure mercury lamp of 1 KW containing all g, h, and i rays, and was irradiated with an illuminance of 100 mJ/cm ^{2, and} no special optical filter was used. The ultraviolet-irradiated thin film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes for development. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to manufacture a color filter. The manufactured color filter had a film thickness of 2.0 μm.

Light resistance The light resistance was measured by measuring the chromaticity and the transmittance of the substrate prepared in the experimental example with a colorimeter (manufactured by Olympus, OSP-200), and measuring the color coordinates of the substrate. After irradiating the light resistance equipment (APS, CPS+ equipment) for 200 hours, the chromaticity and the transmittance were measured again with a colorimeter (manufactured by Olympus, OSP-200).

ΔEab is a value required by the following saturation formula based on the color system of the CIE1976 (L*, a*, b*) space. (Handbook of Color Science, New Edition, edited by Japan Color Society (1985), p. 266).
ΔE*ab={(ΔL) ² +(Δa) ² +(Δb) ² } ^1/2
[Light resistance evaluation criteria]
◯: ΔE*ab value: 3 or less Δ: ΔE*ab value: 3 to 10 or less ×: ΔE*ab value: 10 or more

Experimental Example: Development speed Each of the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was applied on a glass substrate by a spin coating method, and then placed on a heating plate and kept at 100°C. After maintaining the temperature for 3 minutes to form a thin film, the whole film is exposed without a photomask and irradiated with 50 mJ/cm ² of ultraviolet rays, and then the film thickness of the pattern is measured by a film thickness measuring device (DEKTAK6M; manufactured by Veeco). It was measured using. After the thickness measurement was completed, the substrate was again immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development, and then it was confirmed whether or not the self-luminous photosensitive resin composition remained in the non-exposed portion.
[Development speed evaluation criteria]
At the time of development, the time taken for the unexposed area to completely dissolve in the developing solution was measured and shown. When it was not developed, it was shown as "x".

Referring to Table 3, Examples 1 to 5 prepared using the binder resin having a pyran or furan structure according to the present invention have excellent heat resistance and light resistance, and a high developing speed. On the other hand, in the cases of Comparative Examples 1 to 3, it was confirmed that the developing speed was slow and the heat resistance and the light resistance were not all excellent.

The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments and can be modified into various different forms. A person having ordinary knowledge in the technical field can understand that the present invention can be implemented in other specific forms without changing the technical idea and essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive.

1: Backlight 3: Color conversion layer 5: Color filter

Claims (7)

A composition for forming a color conversion layer,
Includes a fluorescent dye, a photopolymerizable compound, a photopolymerization initiator, a binder resin, and a solvent,
Contains no metal complex dye,
The photopolymerization initiator, Ri oxime ester-based photopolymerization initiator der, self-luminous light-sensitive, characterized in der Rukoto least one selected from the group consisting of compounds represented by the following Chemical Formula 1-5 Resin composition :

In Chemical Formula 1,
R ₁ is

Wherein R ₄ is an alkylene group having 1 to ₄ carbon atoms, R ₅ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms,
R ₂ is an alkyl group having 1 to 8 carbon atoms or a phenyl group,
R ₃ is a hydroxy group, or an alkyl group having 1 to 8 carbon atoms, which is substituted or unsubstituted with an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or a diphenyl sulfide group.

In the chemical formula 2,
R ₆ is an alkyl group having 1 to 8 carbon atoms or a phenyl group,
R ₇ is

Wherein R ₈ is an alkylene group having 1 to 4 carbon atoms; R ₉ is an alkyl or cycloalkyl group having 3 to 8 carbon atoms.

In Chemical Formula 3,
X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms,
R ₁₀ to R ₁₂ are each, independently, -R, -OR, -COR, -SR , -CONRR ', or represents -CN, this time, the R and R' is 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, which is selected from the group consisting of a halogen atom and a 5 to 7-membered heterocyclic group. It may be substituted with one or more kinds, and among these, the alkylene portion of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R′ are They may form a ring together,
R _{13 to} R ₁₆ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms,
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,
q represents 0 or 1.

In 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 an arylalkyl having 7 to 40 carbon atoms. And 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 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,
R ₂₉ is

Is .
The self-luminous photosensitive resin composition according to claim 1, wherein the binder resin includes one or more repeating units represented by 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, wherein the aryl group can be substituted with N, O, or S,
n is 0 or 1. The self-luminous photosensitive resin composition according to claim 2 , wherein the binder resin contains all repeating units in which n is 1 and repeating units in which n is 0. The photopolymerization initiator further comprises at least one selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds. The self-luminous photosensitive resin composition described. The self-luminous photosensitive resin composition further comprises at least one photopolymerization initiation auxiliary selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group. Item 1. The self-luminous photosensitive resin composition according to Item 1. Based on the total weight of the solid content of the self-luminous photosensitive resin composition,
Containing 0.1 to 30% by weight of a fluorescent dye, 5 to 60% by weight of a photopolymerizable compound, and 1 to 60% by weight of a binder resin,
The photopolymerization initiator is included in an amount of 0.1 to 40 parts by weight based on a total of 100 parts by weight of the content of the photopolymerizable compound and the binder resin based on the solid content. Self-luminous photosensitive resin composition. On top of the substrate, according to claim 1 a display device comprising a color conversion layer produced by self-luminous light-sensitive resin composition according to any one of 6.

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