KR102204534B1 - Self emission type photosensitive resin composition, and display device comprising color conversion layer prepared thereof - Google Patents

Abstract

The present invention relates to a display device comprising a self-luminous photosensitive resin composition and a color conversion layer prepared therefrom, and more particularly, a fluorescent dye, a photopolymerizable compound, an oxime ester-based photopolymerization initiator, a binder resin, and a magnetic substance comprising a solvent. It relates to a display device including a light-emitting photosensitive resin composition and a color conversion layer prepared therefrom.
The color conversion layer containing the above composition solves the problem of reduction in light efficiency due to the conventional color filter, reduction in light efficiency due to photoinitiators, and yellowing, and maintains high luminance when introduced into a display device, and provides excellent color conversion characteristics and high light efficiency. By securing efficiency, high-quality, vivid picture quality can be realized.

Description

Self-emission photosensitive resin composition, and display device including a color conversion layer prepared therefrom {Self emission type photosensitive resin composition, and display device comprising color conversion layer prepared thereof}

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

Recently, the display industry has undergone a rapid change from a cathode-ray tube (CRT) to a flat panel display represented by plasma display panel (PDP), organic light-emitting diode (OLED), liquid-crystal display (LCD), etc. Among them, LCD is widely used as an image display device used in almost all industries, and its application range is continuously expanding.

In LCD, the transmittance is adjusted as white light generated from the backlight unit passes through the liquid crystal cell, and the three primary colors that pass through the red, green, and blue color filters are mixed to realize full color.

As a light source of the backlight unit, a CCFL (Cold Cathode Fluorescent Lamp) is used. In this case, since the backlight unit must always apply power to the CCFL, power consumption is consumed. In addition, a color gamut of about 70% compared to the conventional CRT and environmental pollution problems due to the addition of mercury are pointed out as disadvantages.

As a substitute for solving the above problem, research on a backlight unit using a light emitting diode (LED) is currently being actively conducted. When the LED is used as a backlight unit, it exceeds 100% of the color reproduction range specification of the National Television System Committee (NTSC), and more vivid image quality can be provided to consumers.

Accordingly, in the same industry, a method is proposed by changing the material and structure of a color filter and an LCD panel to improve the efficiency of a backlight light source.

The color filter forms pixels of each color through a patterning process after applying a dispersion composition including a pigment or a dye, and these pigments and dyes cause a problem of lowering the transmission efficiency of a backlight light source. As a result, the decrease in transmission efficiency lowers the color reproducibility of the display device, thus making it difficult to implement a high-quality screen.

The problem of low color reproducibility can be solved by increasing the light efficiency of the color filter, and thus, a method of introducing a color conversion layer (or a light conversion layer) by increasing the thickness of the color filter or stacking or adjacent to it has been proposed. .

1 is a schematic diagram showing the role of a color conversion layer in a display device. As shown in FIG. 1, a light source generated from the backlight furnace 1 directly increases light efficiency through a color conversion layer 3 and a color filter 5 I can.

As the composition of the color conversion layer, dyes or pigments have been used in the past, but it is difficult to expect improvement in light efficiency with only such dyes and pigments, and rather, a problem of lowering the luminance occurs. Accordingly, the use of a fluorescent material as a material of the color conversion layer 3 has been proposed.

The fluorescent material is excited by blue light emitted from the backlight 1, and emits light in the front direction by changing the wavelength of the blue light to emit white light such as red white light or green white light, resulting in light efficiency. Improves.

A number of patents have been applied for a color conversion layer having a fluorescent material. Among them, Korean Patent Publication No. 2012-0048218 is disposed between the backlight unit and the substrate or on the shutter unit, and transmits incident light in the blue or ultraviolet wavelength band to a predetermined wavelength band. It refers to a display device having a light conversion unit having at least one fluorescent material that converts light of light.

Republic of Korea Patent Publication No. 2013-0083807 proposes a liquid crystal display device with a backlight unit capable of improving light efficiency, and at this time, a phosphor, a quantum dot, a white scattering body, and an electroluminescence are used to improve light efficiency. ) It is proposed to introduce color conversion materials such as materials and photoluminesence materials.

Japanese Patent Laid-Open No. 2013-077825 proposes a method of introducing a color conversion layer made of a green light-emitting phosphor to shape the brightness of a white light-emitting diode (LED).

These patents seek to improve the quality of the display device by introducing a color conversion layer containing a phosphor, etc., and at this time, the method of forming the color conversion layer is not directly mentioned, or even if mentioned, simply disperse in a solvent and then wet coating. It presents a way to do it.

As shown in FIG. 1, the color conversion layer may be formed in a pattern corresponding to each of the red (R) and green (G) pixel portions of the color filter. In this case, a phosphor having a size of several hundred microns for the color conversion layer is dissolved in a solvent. Since it is not in a dispersed state, it is difficult to implement a fine pattern and it is not easy to adjust physical properties such as thickness.

This difficulty can be solved by implementing a fine pattern through a photolithography method using a photosensitive resin composition.

In the case of a conventional photosensitive resin composition, a photoinitiator is essentially used for polymerization.It not only lowers the fluorescence efficiency of the phosphor due to radicals generated from the photoinitiator, but also changes color by the photoinitiator in the post-baking process performed during the photolithography process. It brought new problems, such as the yellowing of the layers.

Korean Patent Publication No. 2012-0048218 Korean Patent Publication No. 2013-0083807 Japanese Patent Publication No. 2013-077825

The present invention is to solve the above problems, by using a specific photopolymerization initiator in a specific content, it exhibits excellent color conversion characteristics and high fluorescence efficiency, and by including a specific binder resin, self-luminescence that can increase the development speed and adhesion It is to provide a photosensitive resin composition.

In addition, another object of the present invention is to provide a display device having a color conversion layer including the self-luminous photosensitive resin composition and capable of realizing high-quality vivid image quality.

In order to achieve the above object, the present invention is a composition for forming a color conversion layer, characterized in that it comprises a fluorescent dye, an antioxidant, a binder resin, a photopolymerizable compound, an oxime ester photopolymerization initiator and a solvent.

In addition, the present invention features a display device including a color conversion layer made of the self-luminous photosensitive resin composition.

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

A display device in which a color conversion layer made of the self-luminous photosensitive resin composition is introduced maintains high luminance, and secures excellent color conversion characteristics and high light efficiency, thereby realizing high-quality vivid image quality.

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

The present invention provides a self-luminous photosensitive resin composition that can be used in 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 caused by the use of the color filter, and is finely formed to correspond to the red (R) and green (G) patterns of the color filter. It consists of a pattern.

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

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

In particular, the present invention proposes a photosensitive resin composition comprising a fluorescent dye and a specific photopolymerization initiator as essential components as a composition of the color conversion layer, and the fluorescence efficiency according to the spontaneous emission of the fluorescent dye leads to overall light efficiency improvement, and photosensitive The resin composition can form a fine pattern, and as an antioxidant, the effect of reducing fluorescence efficiency and preventing yellowing due to the photoinitiator of the photosensitive resin composition is secured.

In more detail, the oxime ester-based initiator of the diphenyl sulfide structure or the oxime ester-based initiator of the carbazole structure according to the present invention is highly sensitive and can reach a sufficient curing rate in a small amount, so that a decrease in fluorescence efficiency can be suppressed.

In addition to the above fluorescent dye and antioxidant, the self-luminous photosensitive resin composition according to the present invention includes a binder resin, a photopolymerizable compound, and a photopolymerization initiator solvent.

Each composition will be described below.

Fluorescent dyes contained in the self-luminous photosensitive resin composition of the present invention are solvents (Solvent), acid (Acid), Basic (Basic), reactive in Color Index [The Society of Dyers [0119] and Colorists publication] Dyes classified as (reactive), direct, disperse, or vat may be mentioned. More specifically, dyes having the following color index (C.I.) numbers may be mentioned, but are not limited thereto.

C.I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C.I. Acid yellow 7, 23, 25, 42, 65, 76;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct yellow 4, 28, 44, 86, 132;

C.I. Dispulse yellow 54, 76;

C.I. Solvent orange 41, 54, 56, 99;

C.I. Acid orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct orange 26;

C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid violet 102;

C.I. Solvent green 1, 5;

C.I. Acid green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1st place.

Typical fluorescent dyes include 3-(2-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6), 3-(2-benzoimidazolyl)-7-diethylaminocoumarin (coumarin 7), and coumarin 135 And coumarin-based dyes such as. In addition, naphthalimide-based dyes such as Solvent Yellow 43, Patent Publication No. 10-2010-0056437, and Solvent Yellow 44 may be used. In addition, various low-molecular luminescent materials and various high-molecular luminescent materials can also be applied.

Quinacridone derivatives such as diethyl quinacridone (DEP); Cyanine pigments such as 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM-1, (I)), DCM-2(II), and 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. Include. In addition, 3-(2-benzothiazolyl)-7-diethylamino coumarin (diethylamino coumarin) (3-(2-benzothiazolyl))-7-diethylamino coumarin ( Coumarin pigments such as coumarin 6), 3-(2-benzoimidazolyl)-7-diethylamino coumarin (coumarin 7), and coumarin 135; It contains a low molecular weight organic fluorescent dye such as a naphthalimide dye such as Solvent Yellow 43 and Solvent Yellow 44. Alternatively, a polymeric fluorescent material typified by polyphenylene, polyarylene, and polyfluorene may be used as a color conversion dye.

In some cases, a mixture of two or more types of pigments may be used as the color conversion pigment. The use of a dye mixture is an effective means when the wavelength shift width is wide, such as at the time of conversion from blue light to red light. The dye mixture may be a mixture of the above-described dyes. Further, a mixture of the above-described dye and the following dye may be used. Quinacridone derivatives such as diethylquinacridone (DEQ); 4-Dicyanomethylene-2-methyl, (p-dimethylaminostyryl)-4H-pyran (DCM-1, (I)), DCM-2(II) and DCJTB(III), etc. Cyanine pigment of; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene ( IV); Xanthenes such as Lumogen F Red, Lumogen F Orange, Lumogen F Yellow, Nile Red(V),) Rhodamine B and Rhodamine 6G xanthene) pigment; And pyridine pigments such as pyridine 1 are preferable.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, and other polyfunctional monomers. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroly. Such as money. 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, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di And pentaerythritol hexa(meth)acrylate. Among these, a bifunctional or higher polyfunctional monomer is preferably used.

The photopolymerizable compound is usually used in the range of 5 to 50% by mass, preferably 7 to 45% by mass, based on the solid content in the self-luminous photosensitive resin composition. When the photopolymerizable compound is included in the above range, the intensity and smoothness of the pixel portion can be improved.

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention has an oxime ester photopolymerization initiator as an essential component. More preferably, it may be represented by the following Chemical Formulas 1 to 9.

[Formula 1]

(In Formula 1,

이고, 이때 R₄는 탄소수 1 내지 4의 알킬렌기이고, R₅는 탄소수 3 내지 8의 알킬 또는 시클로알킬기이고,R ₁ is

And, 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 a C 1 to C 8 alkyl group or a phenyl group,

R ₃ is a hydroxy group or a C 1 to C 8 alkyl group substituted or unsubstituted with a C 1 to C 8 alkyl group, a phenyl group, a benzyl group or a diphenyl sulfide group)

[Formula 2]

(In Chemical Formula 2,

R ₆ is an alkyl group or a phenyl group having 1 to 8 carbon atoms,

이고, 이때 R₈은 탄소수 1 내지 4의 알킬렌기이고; R₉는 탄소수 3 내지 8의 알킬 또는 시클로알킬기이다.)R ₇ is

In this case, 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.)

[Formula 3]

(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 the same as or different from each other, and each independently represents -R, -OR, -COR, -SR, -CONRR' or -CN, wherein R and R'are an alkyl group having 1 to 8 carbon atoms, 6 to 12 aryl groups, C 7 to C 13 aralkyl groups or 5 to 7 membered heterocyclic groups, and these may be substituted with halogen atoms and 5 to 7 membered heterocyclic groups, among which the alkyl group and the alkylene portion of the aralkyl group are unsaturated. It may be interrupted by a bond, an ether bond, a thioether bond, or an ester bond, and R and R'may form a ring together,

R ₁₃ to R ₁₆ are the same as or different from each other, and each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms,

X is a halogen atom or an alkyl group having 1 to 8 carbon atoms,

Y ¹ to Y ³ are the same as or different from each other and are 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, as the alkyl group represented by R and R'in Formula 1, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propy Roxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazol-2'-yl)ethenyl, etc. are mentioned, Among them, an alkyl group having 1 to 8 carbon atoms is preferable.

In addition, examples of the aryl group represented by R and R'include phenyl, tril, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like, among which carbon atom A number of 6 to 12 aryl groups are preferred. In addition, as the aralkyl group represented by R and R′, for example, an aralkyl group having 7 to 13 carbon atoms such as benzyl, chlorobenzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, phenylethenyl, etc. is preferable. Can be lifted. Examples of the heterocyclic group represented by R and R'include preferably a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, and thiophenyl. Further, examples of the ring that can be formed by combining R and R'include preferably a ring having 5 to 7 carbon atoms such as a piperidine ring and a morpholine ring. In addition, R and R'are substituted with halogen elements such as fluorine, chlorine, bromine, and iododo, or are pyridyl, pyrimidyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, or already Dazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, pipera It may be substituted with a heterocyclic group having 5 to 7 carbon atoms such as piperadyl and morpholinyl.

Examples of the halogen atom represented by X include fluorine, chlorine, bromine, and iodine. In addition, the alkyl group represented by X is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, substituted or unsubstituted with a halogen atom. Isooctyl, 2-ethylhexyl, and tert-octyl.

Examples of the halogen atom represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ in the above formula (3) include fluorine, chlorine, bromine, and iodine.

In addition, in Formula 3, the alkyl group represented by R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ is substituted or unsubstituted with a halogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 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 Formula 3 may be preferably the following compound.

As a commercial item having the structure of Formula 3, N-1919 (ADEKA Co., Ltd.) etc. are mentioned.

[Formula 4]

(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, an arylalkyl group having 7 to 40 carbon atoms, 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 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 Period, 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, hydroxy-n - pentyl group, hydroxy-i - pentyl group, hydroxy-n - hexyl group, a hydroxy-i - hexyl group, a hydroxy-methoxy-methyl, hydroxy-methoxy-ethyl, hydroxy-methoxypropyl group, a hydroxy It may be a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group, or a hydroxyethoxyhexyl group.

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

As the fluorene-based initiator used in the present invention, representatively, the following compounds may be exemplified, but not limited to the following examples, and any known in the art as meeting the above conditions may be used.

[Formula 5]

(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 a C 1 to C 8 alkyl group or a phenyl group,

이다.)R ₂₉ is

to be.)

[Formula 6]

(In 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, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. You can do it. Y1 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.)

[Formula 7]

(In Chemical Formula 7,

R ₃₃ , R ₃₄ and R ₃₅ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. May be, X, Y1, m, p and q are the same as in Formula 6,

R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ each independently represent a hydrogen atom, a halogen atom or an alkyl group,

Y2 and Y3 each independently represent an oxygen atom, a sulfur atom, or a selenium atom.)

[Formula 8]

(In Chemical Formula 8,

R ₄₀ , R ₄₁ and R ₄₂ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. May be, X, Y1, m, p and q are the same as in Formula 6,

X'represents a halogen atom or an alkyl group, and r represents an integer of 0-4.)

[Formula 9]

(In Chemical Formula 9,

R ₄₃ , R ₄₄ and R ₄₅ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. May be, X, Y1, m, p and q are the same as in 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 further used in combination within the range not impairing the effects of the present invention. Typically, it is preferable to use at least one compound selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxy) Oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 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]propane-1 -One, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (tert -Butylperoxycarbonyl)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, 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-triazine, and the like.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-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 imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group, and the like. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone. have.

The self-luminous photosensitive resin composition according to the present invention may further include a photopolymerization initiation aid. The self-luminous photosensitive resin composition according to the present invention further contains a photopolymerization initiation aid, thereby further increasing the sensitivity and improving productivity.

The photopolymerization initiation aid may preferably be 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.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone ), 4,4'-bis(diethylamino)benzophenone, etc. 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 Acetic 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, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl) Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. I can.

The photopolymerization initiator may be included in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid content of the self-luminous photosensitive resin composition of the present invention, based on the content of the photopolymerizable compound and the binder resin. When the photopolymerization initiator is included within the above range, it is preferable because the self-luminous photosensitive resin composition is highly sensitive to shorten the exposure time, so that productivity is improved and high resolution can be maintained. Further, the strength of the pixel portion formed by using the composition under the above-described conditions and smoothness on the surface of the pixel portion can be improved. In addition, in the case of the photopolymerization initiation aid, it should contain 10 to 100% by weight, preferably 20 to 100% by weight of the total photopolymerization initiator. If the ratio of the photopolymerization initiator auxiliary agent among the total photopolymerization initiators is less than 10% by weight, the decrease in sensitivity due to the dye cannot be overcome and a short circuit of the pattern is likely to occur during the development process.

In addition, when the photopolymerization initiation aid is further used, the photopolymerization initiation aid is 0.1 to 40% by weight, preferably based on the total solid content of the self-luminous photosensitive resin composition of the present invention, based on the content of the photopolymerizable compound and the binder resin. May contain 1 to 30% by weight. When the amount of the photopolymerization initiating auxiliary agent is in the range of 0.1 to 40% by weight, the sensitivity of the self-luminous photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition is improved.

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 or heat, and acts as a dispersion medium for a 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 any binder resin soluble in an alkaline developer used in the developing step for manufacturing a color filter may be used.

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

[Formula 10]

(In Chemical Formula 10,

R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ are each independently the same as or different from each other,

Hydrogen, a halogen group, a C1-C10 alkyl group; C5 ~ C10 cycloalkyl group, or C6 ~ C20 aryl group, wherein the aryl group can be substituted with N, O or S,

n is 0 or 1.)

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

The alkyl group mentioned in the present invention includes a straight chain or branched type, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n -Octyl, n-decyl, and the like.

Cycloalkyl groups mentioned in the present invention include cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted bornyl, norbornyl and norbornyl, and the like.

Aryl groups mentioned in the present invention include phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, and the like.

At this time, the binder resin may include both a repeating unit in which n is 1 and a repeating unit in which n is 0, and the repeating unit in which n is 1 is a polymerization of a monomer of Formula 11 below, and the repeating unit in which n is 0 is A polymerization of the monomer of Formula 12 will be described in detail below.

By including the binder resin of Formula 10 having a pyran or furan structure as described above, it is advantageous in terms of a process because the developing speed is increased.

In the binder resin, the content ratio of the repeating unit of 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 content. Within the above range, there are advantages of adhesion and permeability.

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

[Formula 11]

(In Chemical Formula 11,

R ₅₀ , R ₅₁ , R ₅₂ , R ₅₃ are each independently the same as or different from each other,

Hydrogen, a halogen group, a C1-C10 alkyl group; C5 ~ C10 cycloalkyl group, or C6 ~ C20 aryl group, wherein the aryl group can be substituted with N, O or S.)

For example, in an embodiment of the present invention, a material satisfying the structure of Formula 11 may be directly prepared or a commercially available product may be purchased and used, and methyl-2-(bromomethyl)-acrylate (manufactured by Aldrich) and It can be obtained by polymerization of triethylamine (manufactured by Aldrich) and methyl-2-(hydroxymethyl)-acrylate (manufactured by Aldrich). As the solvent used for the polymerization, propylene glycol methyl ether (manufactured by TCI) and 2,2'-azobis isobutyronitrile (manufactured by Wako) may be used.

[Formula 12]

(In Formula 12,

R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ are each independently the same as or different from each other,

Hydrogen, a halogen group, a C1-C10 alkyl group; C5 ~ C10 cycloalkyl group, or C6 ~ C20 aryl group, wherein the aryl group can be substituted with N, O or S.)

The copolymer containing the repeating unit of Formula 12 may be polymerized by using a substituted or unsubstituted dihydrofuran, or the same method as in Formula 11, and these materials are directly prepared or used by purchasing a commercially available product. This is possible.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids having one or more carboxyl groups in the molecule. I can.

Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. are mentioned, for example. As an unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) ), mono phthalic acid (2-acryloyloxyethyl), mono phthalic acid (2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. .

These carboxyl group-containing monomers may be used alone or in combination of two or more. Other monomers that can be copolymerized with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxy. Toxoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl 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-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allylacrylic Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Rate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- Unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl, such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; 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; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. And macromonomers to have.

These monomers can be used alone or in combination of two or more. Particularly, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton as other monomers copolymerizable with the carboxyl group-containing monomer are preferable because they tend to lower the relative dielectric constant value. .

These monomers can be used alone or in combination of two or more. When the binder resin is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with this monomer, the content ratio of the constituent units derived from the carboxyl group-containing monomer is a weight ratio based on the total content of the constituent units constituting the copolymer. It is 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight. If the content ratio of the constituent units derived from the carboxyl group-containing monomer is 10 to 50% by weight based on the above criteria, it is preferable because the solubility in the developer is good and the pattern is accurately formed during development. In addition, other copolymerizable carboxyl group-containing monomers are possible. The content of the monomer is 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight, based on the total content of the constituent units constituting the copolymer.

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. When the binder resin is included in the range of 1 to 60% by weight based on the above, it is preferable because solubility is good and pattern formation is excellent.

The binder resin of the present invention preferably has an acid value 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, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually determined by titration using an aqueous potassium hydroxide solution. In addition, the weight average molecular weight in terms of polystyrene (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 ratio is high, the solubility of 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 1.5 to 6.0, more preferably 1.8 to 4.0. A molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.5 to 6.0 because developability is excellent.

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 monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene Alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, 3-methoxy Esters such as methyl oxypropionate, and cyclic esters such as γ-butyrolactone. In the above solvents, from the viewpoint of coating properties and drying properties, preferably, organic solvents having a boiling point of 100° C. to 200° C. in the solvents are mentioned, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid Esters such as ethyl or methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and 3-meth Methyl oxypropionate, etc. are mentioned. These solvents can 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 mass, preferably 70 to 85% by mass, in terms of mass fraction with respect to the total amount of the self-luminous photosensitive resin composition containing the same. If the content of the solvent is within the above range, the coating property can be improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet.

The self-luminous photosensitive resin composition of the present invention includes fillers, other polymer compounds, and pigment dispersants as needed. It is also possible to combine additives such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent. Specific examples of the filler include glass, silica, and alumina. Examples of other polymer compounds specifically include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. have. As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. Each of these may be used alone or in combination of two or more. As the above surfactant, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl peethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes , Polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Megafac (manufactured by Dai Nippon Ink Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), Sol SOLSPERSE (manufactured by Geneva Corporation), EFKA (manufactured by EFKA Chemicals Corporation), PB 821 (manufactured by Ajinomoto Corporation), and the like. As an 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)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane and the like. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-<81>t-butyl-4-methylphenol, and the like. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole and alkoxybenzophenone. Specific examples of the anti-aggregation 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 dissolved by mixing with a solvent in advance. At this time, if necessary, a pigment dispersant is used, and some or all of the binder resin may be blended. To the obtained dispersion (hereinafter, sometimes referred to as a mill base), the rest of the binder resin, the photopolymerizable compound, and the photopolymerization initiator are further added to a predetermined concentration of other components to be used, as well as additional solvents if necessary. A self-luminous photosensitive resin composition is obtained.

As follows, the present invention will be described in more detail based on examples, but the scope of the present invention is not limited to these embodiments by way of example only. The scope of the present invention is indicated in the claims, and furthermore contains the meanings equivalent to the claims record and all modifications within the scope. In addition, "%" and "parts" indicating content below are based on mass unless otherwise noted.

Synthesis Example 1. Binder Resin B1

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube was prepared, and as a monomer dropping lot, benzyl maleimide 74.8 g (0.20 mol), acrylic acid 43.2 g (0.30 mol), and vinyl toluene 118.0 g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring and mixing, and as a dropping tank for a chain transfer agent, 6 g of n-dodecanethiol , PGMEA 24g was put and stirred and mixed.

Thereafter, 395 g of PGMEA was introduced into the flask, 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, dropping of the monomer and chain transfer agent was started from the dropping lot. Dropping is maintained at 90℃, each proceeds for 2h, and after 1h, the temperature is raised to 110℃ and maintained for 3h, and then the gas introduction pipe is introduced to start bubbling of the mixed gas of oxygen/nitrogen = 5/95 (v/v) did. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added into the flask, and the reaction was continued at 110° C. for 8 hours to obtain a binder resin B1 having a solid acid value 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

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, the atmosphere in the flask was changed from air to nitrogen, and then heated to 100°C, and then benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 45.0 g (0.50 mol), azobisisobutyronitrile in a mixture containing 44.5 g (0.10 mol) of monomethacrylate of an isocyclic skeleton and 136 g of propylene glycol monomethyl ether acetate The solution to which 3.6 g was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 100°C for 5 hours.

Then, the atmosphere in the flask was made from nitrogen to air, and glycidyl methacrylate 30 g [0.2 mol, (40 mol% based on the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0.9 g and hydroquinone 0.145 g was put into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a binder resin B2 having a solid acid value 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

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, the atmosphere in the flask was changed from air to nitrogen, and then heated to 100°C, and then 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 of azobis A solution to which 3.6 g of isobutyronitrile was added was added dropwise from the dropping lot to the flask over 2 hours, and stirring was continued at 100°C for 5 hours.

Next, the atmosphere in the flask was made from nitrogen to air, and glycidyl methacrylate 30 g [0.2 mol, (40 mol% based on the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0.9 g and hydroquinone 0.145 g was put into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a binder resin B3 having a solid acid value 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 a Monomer Represented by Formula 11

In a four-necked flask equipped with a dropping funnel, thermometer, cooling tube, and stirrer, 23.3 g of methyl-2-(bromomethyl)-acrylate (manufactured by Aldrich), 15.8 g of triethylamine (manufactured by Aldrich) and methyl propylene glycol 115.0 g of ether (manufactured by TCI) was added and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 90°C, and then methyl-2-(hydroxymethyl)-acrylate (manufactured by Aldrich) 15.1g, 2,2'-azobis isobutyronitrile (manufactured by Wako) 3.2g and propylene A mixed solution of 110.0 g of glycol methyl ether (manufactured by TCI) was added dropwise over 1 hour and polymerization was carried out 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'-azobis isobutyronitrile (manufactured by Wako) was gradually added dropwise over 1 hour. And polymerization for 8 hours, and then allowed to cool to room temperature. After replacing the inside of the four-necked flask with nitrogen, in the flask is glycidyl methacrylate (manufactured by Mitsubishi Rayon) 61.5 parts by weight, tetra-n-butylammonium bromide (manufactured by TCI) 3.6 g and metoquinone (manufactured by Junsei) 0.15 g was added, followed by reaction 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 a Monomer Represented by Formula 12

In a four-necked flask equipped with a dropping funnel, thermometer, cooling tube, and stirrer, 37.5 g of methacrylic acid (manufactured by Kyoeisha), 19.0 g of methyl methacrylate (manufactured by Kyoeisha), 2,5-dihydrofuran (TCI) Product) 9.1 g, and 225.0 g of propylene glycol methyl ether (manufactured by TCI) were added, and the inside of the four-necked flask was replaced with nitrogen. Next, the flask was heated to 70° C., followed by 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 isobuty. A mixed solution of 3.2 g of nitrile (manufactured by Wako) was gradually added dropwise over 1 hour.

After 8 hours of polymerization, the resultant was allowed to cool to room temperature, and the inside of the four-necked flask was replaced with nitrogen. Then, 61.5 parts by weight of glycidyl methacrylate (manufactured by Mitsubishi Rayon), tetra-n-butylammonium bromide (manufactured by TCI) ) 3.6 g and 0.15 g of metoquinone (manufactured by Junsei) were added and reacted at 80° C. for 12 hours to add GMA 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: Preparation of color conversion layer

After the solvent was added to the mixer, a dye, a binder resin, a photopolymerizable compound, and a photopolymerization initiator were added thereto, and uniformly mixed through stirring to prepare a self-luminous photosensitive resin composition. At this time, the composition follows the composition of Table 1 and Table 2 below.

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

Subsequently, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure amount (365 nm) of 40 mJ/cm 2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (brand name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

The UV-irradiated thin film was developed in a developing solution of a KOH aqueous solution having a pH of 12.5 using a spray developer 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 prepared above was 3.0 μm.

Composition (% by weight) Example One 2 3 4 5 dyes A 0.4 0.4 0.4 0.4 0.4 Binder resin B1 9.24 - - - - B2 - 9.24 - - - B3 - - 9.24 - - B4 - - - 9.24 - B5 - - - - 9.24 Photopolymerizable compound C 9.24 9.24 9.24 9.24 9.24 Photopolymerization initiator D1 0.75 0.75 0.75 D2 0.75 D3 0.75 D4 menstruum E Balance Balance Balance Balance Balance A: Kuramine 6
B1: Resin prepared in Synthesis Example 1
B2: Resin prepared in Synthesis Example 2
B3: Resin prepared in Synthesis Example 3
B4: Resin prepared in Synthesis Example 4
B5: Resin prepared in Synthesis Example 5
C: dipentaerythritol hexaacrylate
(Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D1: TR-PBG-305 (Tronly company)
D2: Irgacure OXE-01 (BASF company)
D3: N-1919 (Tronly)
D4: Irgacure 369 (Ciba company)
E: Propylene glycol monomethyl ether acetate

Composition (% by weight) Comparative example One 2 3 dyes A 0.4 0.4 0.4 Binder resin B1 9.24 B2 9.24 B3 9.24 Photopolymerizable compound C 9.24 9.24 9.24 Photopolymerization initiator D1 0.05 D2 50 D3 D4 0.75 menstruum E Balance Balance Balance A: Kuramine 6
B1: Resin prepared in Synthesis Example 1
B2: Resin prepared in Synthesis Example 2
B3: Resin prepared in Synthesis Example 3
C: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D1: TR-PBG-305 (Tronly company)
D2: Irgacure OXE-01 (BASF company)
D3: N-1919 (Tronly)
D4: Irgacure 369 (Ciba company)
E: Propylene glycol monomethyl ether acetate

Experimental Example: Measurement of luminescence intensity

In order to check whether the fluorescence efficiency of the color conversion layers obtained in Examples 1 to 5 and Comparative Examples 1 to 3 is increased, using a quantum efficiency meter (QE-1000, manufactured by Otsuka Corporation), the light emission PL for each coated substrate Was measured. At this time, the obtained results are shown in Table 3 below, and at this time, the higher the measured light emission intensity, the higher the fluorescence efficiency.

Luminous intensity (λmax: 500) Example 1 13632 Example 2 12272 Example 3 13555 Example 4 14000 Example 5 13700 Comparative Example 1 9448 Comparative Example 2 9200 Comparative Example 3 8100

Referring to Table 3, since Examples 1 to 5 have higher luminous intensity values than Comparative Examples 1 to 3, it can be seen that Examples 1 to 5 have excellent fluorescence efficiency.

Experimental Example: Heat resistance evaluation

A color filter was manufactured using the photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was coated on a 2-inch-angled glass substrate (manufactured by Corning, "EAGLE XG") by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Formed. Subsequently, a test photomask having a pattern for changing the transmittance in a stepwise shape in the range of 1 to 100% and a line/space pattern of 1 µm to 50 µm was placed on the thin film, and the interval with the test photo mask was 100 µm. Was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass plate on which the thin film was applied was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

Heat resistance

Heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230° C. for 120 minutes. △Eab is the value required by the saturation formula below by the CIE 1976 (L*, a*, b*) spatial color system. (The Color Science Handbook, New edition of the Japan Color Society edition (Showa 60) p.266).

△E*ab = {(△L)2 +(△a)2+(△b)2}1/2

[Heat resistance evaluation criteria]

○: △E*ab value: 3 or less

△: ΔE*ab value: 3 to 10 or less

X: △E*ab value: more than 10

Experimental Example: Light fastness evaluation

A color filter was manufactured using the photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3. Specifically, each of the above self-luminous photosensitive resin compositions was coated on a 2-inch-angled glass substrate (manufactured by Corning, "EAGLE XG") by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Formed. Subsequently, a test photomask having a pattern for changing the transmittance in a stepwise shape in the range of 1 to 100% and a line/space pattern of 1 µm to 50 µm was placed on the thin film, and the interval with the test photo mask was 100 µm. Was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass plate on which the thin film was applied was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

Light resistance

Light fastness was measured with a colorimeter (Olympus, OSP-200) for the chromaticity and transmittance of the substrate prepared in the above experimental example. It measured again with (Olympus company make, OSP-200).

△Eab is the value required by the saturation formula below by the CIE 1976 (L*, a*, b*) spatial color system. (The Color Science Handbook, New edition of the Japan Color Society edition (Showa 60) p.266).

△E*ab = {(△L)2 +(△a)2+(△b)2}1/2

[Lightfastness evaluation criteria]

○: △E*ab value: 3 or less

△: △E*ab value: 3 to 10 0 or less

X: △E*ab value: more than 10

Experimental example: development speed

Each of the colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100°C for 3 minutes to form a thin film without a photomask. After irradiation of 50mJ/cm2 of ultraviolet rays by front exposure, the film thickness of the pattern was measured using a film thickness measuring apparatus (DEKTAK 6M; manufactured by Veeco). The substrate on which the thickness measurement was completed was further dipped in a developing solution of a KOH solution having a pH of 10.5 for 80 seconds to develop, and then it was confirmed whether or not the self-luminous photosensitive resin composition remained in the non-exposed portion.

[Development speed evaluation criteria]

The time taken for the unexposed part to completely dissolve in the developer during development was measured and shown. When the phenomenon does not occur, it is indicated by'x'.

Heat resistance Light resistance Development speed Example 1 O O 16 Example 2 O O 17 Example 3 O O 16 Example 4 O O 15 Example 5 O O 18 Comparative Example 1 X △ 25 Comparative Example 2 X △ 23 Comparative Example 3 △ X 24

Referring to Table 3, it can be seen that Examples 1 to 5 prepared using a binder resin containing a pyran or furan structure according to the present invention have excellent heat resistance and light resistance, and a rapid development speed. On the other hand, in the case of Comparative Examples 1 to 3, it can be seen that the development speed is also slow, and both heat resistance and light resistance are not excellent.

The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, but may be modified into various different forms, and those having ordinary knowledge in the technical field to which the present invention pertains. It will be understood that the present invention can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

1: substrate
3: color conversion layer
5: color filter

Claims (8)

As a composition for forming a color conversion layer,
Including a fluorescent dye, a photopolymerizable compound, a photoinitiator, a binder resin and a solvent,
The photopolymerization initiator is an oxime ester photopolymerization initiator, and is one or more selected from the group consisting of compounds represented by the following formulas 1 to 9,
The composition is a self-luminous photosensitive resin composition, characterized in that it does not contain a dye or pigment other than the fluorescent dye.
[Formula 1]

(In Formula 1,
R ₁ is

And, 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 a C 1 to C 8 alkyl group or a phenyl group,
R ₃ is a hydroxy group or a C 1 to C 8 alkyl group substituted or unsubstituted with a C 1 to C 8 alkyl group, a phenyl group, a benzyl group or a diphenyl sulfide group)
[Formula 2]

(In Chemical Formula 2,
R ₆ is an alkyl group or a phenyl group having 1 to 8 carbon atoms,
R ₇ is

In this case, 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.)
[Formula 3]

(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 the same as or different from each other, and each independently represents -R, -OR, -COR, -SR, -CONRR' or -CN, wherein R and R'are an alkyl group having 1 to 8 carbon atoms, 6 to 12 aryl groups, C 7 to C 13 aralkyl groups or 5 to 7 membered heterocyclic groups, and these may be substituted with halogen atoms and 5 to 7 membered heterocyclic groups, among which the alkyl group and the alkylene portion of the aralkyl group are unsaturated. It may be interrupted by a bond, an ether bond, a thioether bond, or an ester bond, and R and R'may form a ring together,
R ₁₃ to R ₁₆ are the same as or different from each other, and each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms
Y ¹ to Y ³ are the same as or different from each other and are 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)
[Formula 4]

(In 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, an arylalkyl group having 7 to 40 carbon atoms, a hydrogen having 1 to 20 carbon atoms A hydroxyalkyl group, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms)
[Formula 5]

(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 a C 1 to C 8 alkyl group or a phenyl group,
R ₂₉ is

to be.)
[Formula 6]

(In 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, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. You can do it. Y1 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.)
[Formula 7]

(In Chemical Formula 7,
R ₃₃ , R ₃₄ and R ₃₅ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. You can do it,
X, Y1, m, p and q are the same as in Formula 6,
R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ each independently represent a hydrogen atom, a halogen atom or an alkyl group,
Y2 and Y3 each independently represent an oxygen atom, a sulfur atom, or a selenium atom.)
[Formula 8]

(In Chemical Formula 8,
R ₄₀ , R ₄₁ and R ₄₂ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring. You can do it,
X, Y1, m, p and q are the same as in Formula 6,
X'represents a halogen atom or an alkyl group, and r represents an integer of 0-4.)
[Formula 9]

(In Chemical Formula 9,
R ₄₃ , R ₄₄ and R ₄₅ each independently represent R, OR, COR, SR, CONRR' or CN, R and R'represent an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, and these are halogen atoms and/ Or it may be substituted with a heterocyclic group, of which the alkylene moiety 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′ together form a ring You can do it,
X, Y1, m, p and q are the same as in Formula 6,
X'' represents a halogen atom or an alkyl group, and s represents an integer of 0-4.) delete The method of claim 1,
The binder resin is a self-luminous photosensitive resin composition, characterized in that it contains one or more repeating units of the following formula (10):
[Formula 10]

(In Chemical Formula 10,
R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ are each independently the same as or different from each other,
Hydrogen, a halogen group, a C1-C10 alkyl group; C5 ~ C10 cycloalkyl group, or C6 ~ C20 aryl group, wherein the aryl group can be substituted with N, O or S,
n is 0 or 1.) The method of claim 3,
The binder resin includes both a repeating unit in which n is 1 and a repeating unit in which n is 0. The method of claim 1,
The photopolymerization initiator further comprises an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, and a thioxanthone-based compound. The method of claim 1,
An amine compound, a carboxylic acid compound, and an organosulfur compound having a thiol group, further comprising at least one photopolymerization initiating auxiliary agent. The method of claim 1,
With respect to the solid content in the self-luminous photosensitive resin composition,
A self-luminous photosensitive resin composition comprising 0.1 to 10% by weight of a fluorescent dye, 5 to 50% by weight of a photopolymerizable compound, 0.1 to 40% by weight of a photoinitiator, and 1 to 60% by weight of a binder resin. A display device comprising a color conversion layer made of the self-luminous photosensitive resin composition according to any one of claims 1 and 3 to 7, on a substrate.

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