KR102607871B1 - Self emission type photosensitive resin composition, color filter comprising color conversion layer using the same and display device - Google Patents

Abstract

The present invention is a self-luminous photosensitive resin composition that has excellent fluorescence efficiency and reliability by including a colorant containing two or more types of red fluorescent dyes, and can produce a color conversion layer, color filter, or image display device with excellent color reproduction rate. It's about.

Description

Self-luminous photosensitive resin composition, color filter and image display device including a color conversion layer using the same {SELF EMISSION TYPE PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER COMPRISING COLOR CONVERSION LAYER USING THE SAME AND DISPLAY DEVICE}

The present invention relates to a self-luminous photosensitive resin composition, a color filter including a color conversion layer using the same, and an image display device.

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

LCD's transmittance is adjusted as white light generated from the backlight unit passes through the liquid crystal cell, and the three primary colors passing through the color filters of red, green, and blue are mixed to achieve full color.

CCFL (Cold Cathode Fluorescent Lamp) is used as the light source of the backlight unit, but in this case, the backlight unit must always supply power to the CCFL, which causes the problem of power consumption. In addition, compared to existing CRTs, a color reproduction rate of about 70% and environmental pollution problems due to the addition of mercury are pointed out as disadvantages.

As a replacement to solve the above problems, research is currently being actively conducted on backlight units using LEDs (Light Emitting Diodes). When using LED as a backlight unit, it can exceed 100% of the NTSC (National Television System Committee) color reproduction range specification, providing consumers with more vivid picture quality.

Accordingly, in the same industry, methods are being proposed to improve the efficiency of the backlight light source by changing the materials and structure of the color filter and LCD panel.

A color filter forms pixels of each color through a patterning process after applying a dispersion composition containing pigment or dye. These pigments and dyes cause the problem of lowering the transmission efficiency of the backlight light source. The decrease in transmission efficiency ultimately lowers the color reproducibility of the display device, ultimately making it difficult to implement a high-quality screen. Therefore, research is being conducted to further improve color reproducibility and optical characteristics.

In this regard, Republic of Korea Patent Publication No. 10-2017-0026245 describes a fluorescent dye containing a novel perylene-based compound, and the fluorescent dye has solubility in organic solvents, durability, thermal stability, and luminescent properties. Although it is described as excellent, there is a problem in that the fluorescent dye alone does not satisfy the performance requirements for high color reproduction that are recently required.

In addition, Korean Patent Publication No. 10-2010-0056437 includes a process of forming a color conversion layer that absorbs light of a specific wavelength and outputs light containing a different wavelength from the absorbed wavelength, thereby making the diffusion of ink more effective. There is a description of a manufacturing method of a color conversion filter that can manufacture an organic EL display capable of preventing high-definition multicolor display, but this has the problem of poor thermal or optical stability due to the inclusion of green or yellow fluorescent dye. there is.

Republic of Korea Patent Publication No. 10-2017-0026245 (2017.03.08.) Republic of Korea Patent Publication No. 10-2010-0056437 (May 27, 2010)

The present invention is intended to solve the above problems, and provides a highly reliable self-luminous photosensitive resin composition that has excellent fluorescence efficiency, enables the production of color conversion layers, color filters, or image display devices capable of high color reproduction, and has excellent reliability. It is for that purpose.

The self-luminous photosensitive resin composition of the present invention for achieving the above object is characterized by including a colorant containing two or more types of red fluorescent dyes.

In addition, the color conversion layer of the present invention is characterized by comprising a cured product of the above-described self-luminous photosensitive resin composition.

Additionally, the color filter of the present invention is characterized by including the color conversion layer described above.

Additionally, the image display device of the present invention is characterized by including the color filter described above.

The self-luminous photosensitive resin composition of the present invention has the advantage of excellent fluorescence efficiency and reliability, and therefore the color conversion layer, color filter, or image display device containing the cured product of the self-luminous photosensitive resin composition has the advantage of excellent color reproducibility. there is.

Figure 1 is an illustration of a color filter including a color conversion layer.

In the present invention, when a member is said to be located “on” another member, this includes not only the case where a member is in direct contact with another member, but also the case where another member is interposed between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

Each functional group described in the present invention may be independently substituted or unsubstituted, and the 'substitution' refers to, for example, deuterium, halogen group, nitrile group, alkyl group, cycloalkyl group, akenyl group, aryl group, heteroaryl It may mean being substituted with one or more groups selected from the group consisting of an alkoxy group, an ether group, a thioether group, and a mercapto group, but is not limited thereto.

In the present invention, the 'halogen group' may include, for example, fluorine, chlorine, bromine, or iodine.

In the present invention, the 'alkyl group' may be straight chain or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 40, for example, 1 to 20. The alkyl group is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, Neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl Examples include, but are not limited to, these.

In the present invention, the number of carbon atoms of the 'cycloalkyl group' is not particularly limited, but may be 3 to 30, for example, 3 to 20. The cycloalkyl group includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., but is not limited thereto.

In the present invention, the 'alkoxy group' includes, for example, methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group, etc. However, it is not limited to this.

In the present invention, an 'alkenyl group' refers to an unsaturated hydrocarbon group that is straight chain or branched and contains at least one carbon-carbon double bond, and the number of carbon atoms is not particularly limited, but may be, for example, 2 to 30. The alkenyl group includes, for example, ethenyl, vinyl, propenyl, allyl, isopropenyl, butenyl, isobutenyl, t-butenyl, n-pentenyl, and n-hexenyl, but is limited thereto. It doesn't work.

In the present invention, 'cyclo alkenyl group' refers to a cyclic alkenyl group, and the number of carbon atoms is not particularly limited, but may be, for example, 3 to 30.

In the present invention, an 'alkynyl group' refers to a straight or branched chain, unsaturated hydrocarbon group containing at least one carbon-carbon triple bond, and the number of carbon atoms is not particularly limited, but may be, for example, 2 to 30.

In the present invention, 'aryl group' refers to a monovalent group of an aromatic hydrocarbon or an aromatic hydrocarbon derivative. The aromatic hydrocarbon refers to a compound containing a planar ring in which pi electrons are fully conjugated, and a group derived from an aromatic hydrocarbon refers to a structure in which an aromatic hydrocarbon or a cyclic aliphatic hydrocarbon is condensed with an aromatic hydrocarbon. In addition, the aryl group also includes a monovalent group in which two or more aromatic hydrocarbons or derivatives of aromatic hydrocarbons are linked together. The number of carbon atoms of the aryl group is not particularly limited, but may be 6 to 60, for example, 6 to 40. The aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, and quarterphenyl group, and examples of the polycyclic aryl group include naphthyl group and anthracenyl group. , phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, tetracenyl group, chrysenyl group, fluorenyl group, indenyl group, acenaphthyl group, benzofluorenyl group, etc. However, it is not limited to this.

In the present invention, 'heteroaryl group' refers to an aromatic heterocycle. Here, 'aromatic heterocycle' refers to a group of an aromatic ring or a derivative of an aromatic ring, and a group containing at least one of N, O, and S as a heteroatom in the ring. The derivatives of the aromatic ring include all structures in which an aromatic ring or an aliphatic ring is condensed with an aromatic ring. The number of carbon atoms of the heteroaryl group is not particularly limited, but may be 2 to 60, for example, 2 to 40. The heteroaryl group includes, for example, thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, and pyrimidinyl group. , triazinyl group, triazolyl group, acridinyl group, carbolinyl group, acenaphthoquinoxalinyl group, indenoquinazolinyl group, indenoisoquinolinyl group, indenoquinolinyl group, pyridoindolyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinolinyl group, indolyl group, carbamine Zolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, dibenzofuranyl group, phenanthrolinyl group, Examples include, but are not limited to, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenoxazinyl group, phenothiazinyl group, and dibenzofuranyl group. The heteroaryl group includes an aliphatic heteroaryl group and an aromatic heteroaryl group.

In the present invention, the 'arylamine group' may be substituted or unsubstituted, for example, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methylnaphthylamine, Examples include, but are not limited to, 2-methylbiphenylamine, 9-methylanthracenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, and phenyltolylamine.

In the present invention, 'heterocyclic group' refers to a cyclic chemical group having one or more atoms selected from N, O, and S, and the remaining atom(s) are C atom(s). A ‘heterocyclic group’ is a single ring or multiple ring. When the 'heterocyclic group' is aromatic, it is called a 'heteroaryl group'. Heterocyclic groups may include 4-, 5-, 6-, 7-, or 8-membered rings. Examples of the heterocyclic group include pyrrolidinyl group, piperidinyl group, piperazinyl group, morpholino group, thiomorpholino group, homopiperidinyl group, chromanyl group, isochromanyl group, chromenyl group, pyrrolyl group, and furanyl group. Nyl group, thienyl group, pyrazolyl group, imidazolyl group, furazanyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, pyranyl group, indolyl group, isoindolyl group, indazolyl group, purinyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, pteridinyl group, quinolizinyl group, benzoxa Examples include, but are not limited to, zinyl group, carbazolyl group, phenazinyl group, phenothiazinyl group, and phenanthridinyl group.

Hereinafter, the present invention will be described in more detail.

< self-luminous Photosensitive resin composition>

The self-luminous photosensitive resin composition according to one aspect of the present invention includes a colorant containing two or more types of red fluorescent dyes, and thus has excellent fluorescence efficiency and reliability such as heat resistance or light resistance, and as a result, the self-luminous photosensitive resin composition There is an advantage in that the color conversion layer, color filter, or image display device containing the cured resin composition has excellent color reproduction rate.

coloring agent

Fluorescent dyes are luminescent substances that emit light of a unique wavelength by absorbing energy in the form of light or electricity from the outside. Compared to general dyes, fluorescent dyes have a diverse luminescence spectrum, excellent quantum efficiency, and are cost-effective, making them highly useful as light conversion devices. In particular, when realizing high-definition color display, it is advantageous to increase the concentration of the color conversion material (e.g., dye) to increase the absorbance of the absorbed light in the color conversion layer to obtain high converted light luminance. When the concentration of the color conversion material is increased in this way, the energy absorbed by the light emitted from the organic EL device repeatedly moves between the molecules of the color conversion material, causing concentration quenching in which the color conversion material molecules are deactivated without emitting light. This phenomenon occurs. Therefore, in order to suppress this concentration quenching, the color conversion material must be dissolved or dispersed in some medium to lower its concentration. If the concentration of the color conversion material is excessively reduced, the absorbance of the light to be absorbed decreases, thereby maintaining sufficient converted light intensity. can't get it Therefore, there is an effect of suppressing the concentration quenching phenomenon by using a fluorescent dye with a diverse luminescence spectrum and excellent quantum efficiency. However, due to the continuous increase in high-definition conditions, there is a problem that the required high-definition conditions cannot be satisfied with a method simply including fluorescent dye. Therefore, in order to solve this problem, a method has been devised to improve color conversion efficiency by mixing yellow or green fluorescent dye with red fluorescent dye. However, when yellow or green fluorescent dye is used, heat or light There were problems with poor reliability (light fastness, heat resistance), such as decreased fluorescence.

Therefore, the self-luminous photosensitive resin composition according to one aspect of the present invention includes a colorant containing two or more types of red fluorescent dyes and does not contain, for example, yellow or green fluorescent dyes, and thus has excellent fluorescence efficiency. In addition, it has excellent reliability such as heat resistance or light resistance.

The above two or more types of red fluorescent dyes refer to the case where two or more different types of red fluorescent dyes are included among the red dyes used in the industry. In this case, the types of red dyes are specified in the industry. Those used in can be used without any particular restrictions.

For example, the red fluorescent dye may include a first fluorescent dye and a second fluorescent dye, and part or all of the emission wavelength region of the first fluorescent dye and the absorption wavelength region of the second fluorescent dye overlap. In this case, the 'part' may mean that the area where the emission wavelength region and the absorption wavelength region overlap is more than 1/3 of the total area of the emission wavelength region or the absorption wavelength region. there is. If the range of the overlapping area does not satisfy the above range, fluorescence efficiency may be reduced. In this way, when using two or more types of red fluorescent dyes in which part or all of the emission wavelength region and the absorption wavelength region overlap, the first fluorescent dye absorbs the incident light incident on the color conversion layer from the light source, and the absorbed By transferring energy to the second fluorescent dye, the luminescence phenomenon of the second fluorescent dye can be improved, that is, the fluorescence efficiency can be further improved, and if the yellow or green fluorescent dye is not included, reliability (heat resistance or light resistance) can be improved. It can be improved further.

As an example, the emission wavelength range of the first fluorescent dye may be 500 to 610 nm, preferably 550 to 610 nm, and the absorption wavelength range of the second fluorescent dye may be 570 to 640 nm, preferably may be 600 to 630 nm. In this way, when the emission wavelength region of the first fluorescent dye and the absorption wavelength region of the second fluorescent dye are within the above-mentioned range, there is an advantage in that the fluorescence efficiency of the color conversion layer can be further improved.

The weight ratio of the first fluorescent dye to the second fluorescent dye may vary depending on the degree of overlap between the emission wavelength region of the first fluorescent dye and the absorption wavelength region of the second fluorescent dye, which is specifically limited in the present invention. However, for example, it may be 99:1 to 1:99, preferably 90:10 to 60:40, and more preferably 80:20 to 70:30. When the mixing ratio of the first fluorescent dye and the second fluorescent dye is within the above-mentioned range, there is an advantage of further improving the fluorescence efficiency of the self-luminous photosensitive resin composition containing it, and when it is outside the above range, energy transfer occurs. If this does not occur sufficiently, fluorescence efficiency may decrease and problems with concentration quenching may occur.

The first fluorescent dye can further improve fluorescence efficiency and can more easily satisfy the above-mentioned wavelength range, for example, dipyromethene-based compounds, rhodamine-based compounds, and dicyanomethylene (DCM)-based compounds. and perylenediimide-based compounds.

The dipyromethene-based compound may include, for example, a compound represented by the following formula (1).

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently hydrogen, an alkyl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkoxyaryl group, an alkylthio group, Aryl ether group, arylthioether group, aryl group, haloaryl group, heterocyclic group, halogen group, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, It is an amino group, nitro group, silyl group, or siloxanyl, or is connected to an adjacent substituent to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon or hetero ring,

Wherein L is hydrogen, alkyl group, cycloalkyl group, arylalkyl group, alkylaryl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkoxyaryl group, alkylthio group, arylether group, arylthioether group, aryl group, haloaryl group, heterocyclic group, halogen group, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group. or siloxanyl, or is connected to an adjacent substituent to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon or hetero ring;

where m is an integer from 1 to 3,

M is the m-valent metal atom, and is boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc or platinum,

R ₃ to R ₇ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an amine group, or a substituted or unsubstituted arylalkenyl group, and the substituted alkyl group is substituted with a halogen atom, The substituted aryl group is substituted with a hydroxy group, an alkyl group, or an alkoxy group, and the substituted arylalkenyl group is substituted with an alkoxy group).

Examples of the compound represented by Formula 1 include boron-dipyrromethene-based compounds, and examples of the boron-dipyrromethene-based compounds include compounds represented by the following Chemical Formulas 1-1 to 1-20, etc. can be mentioned.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 1-17]

[Formula 1-18]

[Formula 1-19]

[Formula 1-20]

(In Formulas 1-1 to 1-20, MeO refers to a methoxy group and OEt refers to an ethoxy group).

The rhodamine-based compound may include, for example, a compound represented by the following formula (2), and in this case, there is an advantage in that fluorescence efficiency can be more easily improved.

[Formula 2]

(In Formula 2 above,

R ₈ and R ₉ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,

R ₁₀ to R ₁₁ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,

R ₁₂ to R ₁₃ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group).

The dicyanomethylene-based compound may include, for example, a compound represented by the following formula (3), and in this case, there is an advantage in that fluorescence efficiency can be more easily improved.

[Formula 3]

(In Formula 3 above,

R ₁₄ and R ₁₅ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,

R ₁₆ is hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group).

The perylenediimide-based compound may include, for example, a compound represented by the following formula (4). In this case, there is an advantage in that fluorescence efficiency can be more easily improved.

[Formula 4]

(In Formula 4 above,

R ₁₇ and R ₁₈ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,

R ₁₉ to R ₂₂ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group).

The compound represented by Formula 4 may include, for example, a compound represented by Formula 5 below.

[Formula 5]

For example, the second fluorescent dye may include a perylenebisimide-based compound represented by the following formula (6). In this way, the compound represented by Formula 6 can improve fluorescence efficiency even at high concentrations without quenching phenomenon through the steric hindrance effect of the substituent, can increase solubility in solvents, and can be expected to have excellent chemical, thermal, and optical stability. There are process advantages.

[Formula 6]

(In Formula 6 above,

R ₂₃ and R ₂₄ are each independently, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl,

R ₂₅ to R ₂₇ are each independently hydrogen, a C1 to C10 straight or branched alkyl group, a C6 to C18 aryl group, a C7 to C18 arylalkyl group, a C1 to C18 alkoxy group, or a complex group with 1 to 30 atoms. It is a ventilation or halogen group,

x, y, z are integers from 1 to 5,

When x, y, and z are 2 or more, additional substituents R ₂₅ to R ₂₇ may be the same or different from each other).

Examples of the compound represented by Formula 6 include compounds represented by the following Formulas 6-1 to 6-9. In this case, the expected effect is further improved by including the above-described perylenebisimide-based compound. It can be.

[Formula 6-1]

[Formula 6-2]

[Formula 6-3]

[Formula 6-4]

[Formula 6-5]

[Formula 6-6]

[Formula 6-7]

[Formula 6-8]

[Formula 6-9]

The colorant may be included in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, and more preferably 0.1 to 15% by weight, based on the total solid content in the self-luminous photosensitive resin composition. When the content range of the colorant is within the above-mentioned range, fluorescence efficiency can be further improved, solubility in solvents can be improved, which can be advantageous in terms of processability, reliability such as heat resistance or light resistance can be further improved, and the If the range is exceeded, aggregation of the fluorescent dye may occur, which may reduce the fluorescence efficiency, and defects may appear on the surface during curing.

The self-luminous photosensitive resin composition of the present invention may further include fluorescent dyes, general pigments, or general dyes other than green and yellow fluorescent dyes to the extent that the effect is not impaired, and in this case, the green and yellow fluorescent dyes are used. Except for fluorescent dyes, general pigments or general dyes, those used in the industry can be used without any particular restrictions.

The self-luminous photosensitive resin composition according to an embodiment of the present invention may further include one or more selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.

Alkali soluble resin

The alkali-soluble resin generally has reactivity and alkali solubility under the action of light or heat, and can act as a dispersant for the colorant described above. In the present invention, the alkali-soluble resin functions as a binder resin for the colorant described above. Any resin that is soluble in the alkaline developer used in the development step during the process for producing the color conversion layer can be used without particular restrictions.

Examples of the alkali-soluble resin include a carboxyl group-containing monomer and a copolymer of another monomer that can be copolymerized with the monomer. Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids, etc., which have one or more carboxyl groups in the molecule. there is. Here, examples of unsaturated monocarboxylic acids 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, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate. ), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), etc. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both terminals, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. . These carboxyl group-containing monomers can be used individually or in combination of two or more types. Other monomers copolymerizable with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. Toxystyrene, 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-butylacrylate, 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-hydroxypropyl acrylate Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Latex, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Latex, 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-hydroxyethyl acrylamide, 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 polymers of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butylacrylate, poly-n-butyl methacrylate, and polysiloxane, with a monoacryloyl group or monomethacryloyl group at the end of the molecular chain. Examples include large monomers having . These monomers can be used individually or in combination of two or more types. In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as monomers with a norbornyl skeleton, monomers with an adamantane skeleton, and monomers with a rosin skeleton are preferred because they tend to lower the specific dielectric constant value. You can.

The acid value of the alkali-soluble resin is not particularly limited, but may be, for example, 20 to 200 mgKOH/g. If the acid value is within the above range, the solubility in the developer is improved, so that the non-exposed portion can be easily dissolved and the sensitivity can be increased, and as a result, the pattern of the exposed portion remains during development, and the film remaining ratio can be improved. . Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution. In addition, the alkali-soluble resin has a polystyrene conversion weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) of 3,000 to 200,000, preferably may be 5,000 to 100,000. If the weight average molecular weight is within the above range, the hardness and residual film rate of the cured product of the self-luminous photosensitive resin composition containing it can be improved, and the resolution can be improved due to excellent solubility of non-exposed parts in the developer.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin may be 1.5 to 6.0, preferably 1.8 to 4.0, but is not limited thereto, and the molecular weight distribution is If contained within the above-mentioned range, developability may be improved.

According to one embodiment of the present invention, the alkali-soluble resin may be included in an amount of 5 to 85% by weight, preferably 10 to 70% by weight, based on the total solid content in the self-luminous photosensitive resin composition. When the content of the alkali-soluble resin is contained within the above-mentioned range, the solubility in the developer is sufficient to suppress the generation of development residues on the substrate in the non-pixel portion, and the occurrence of film reduction in the pixel portion of the exposed portion during development is prevented. There is an advantage in that the missingness of non-pixel parts can be improved by suppressing it. If the alkali-soluble resin is contained less than the above-mentioned range, residues or missing patterns may occur during the development process, and if it exceeds the above range, it may not be easy to use as a photosensitive resin composition.

photopolymerizability compound

The photopolymerizable compound refers to a compound that can be polymerized by the action of a photopolymerization initiator, which will be described later, and may include monofunctional monomers, difunctional monomers, or other polyfunctional monomers, but the type is not particularly limited in the present invention. Those used as photopolymerizable compounds in the art can be used without particular restrictions.

The monofunctional monomers include, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpy. Lolidon, etc. can be mentioned.

The bifunctional monomers include, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

The other polyfunctional monomers include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. late, dipentaerythritol hexa(meth)acrylate, etc.

The above-mentioned monomers are not limited to those mentioned above, and they can be used individually or in a mixture of two or more types, and among these, polyfunctional monomers having two or more functions can be preferably used.

According to one embodiment of the present invention, the photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total solid content in the self-luminous photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, the strength or smoothness of the color conversion layer formed therefrom may be improved.

light curing initiator

The type of the photopolymerization initiator is not particularly limited in the present invention, and any photopolymerization initiator that is used in the art may be used without particular limitation.

The photopolymerization initiator includes, for example, acetophenone-based compounds, active radical generators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, triazine-based compounds, acid generators, sensitizers, etc., and acetophenone-based compounds. An argument may be preferably used, but is not limited to this.

The acetophenone-based compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)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[4-(1-methylvinyl)phenyl]propan-1-one oligomers, and the like, and preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

The benzophenone-based compounds include, for example, benzophenone, o-benzoylmethyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (t -Butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

The thioxanthone-based compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4. -Propoxy oxanthone, etc. can be mentioned.

The triazine-based compound may be used as an active radical generator that generates active radicals, but it can also be used as an acid generator because it generates acid together with the active radicals. The triazine-based compounds include, for example, 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-(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-(3,4dimethoxyphenyl)ethenyl]-1,3,5-tri Ajin, etc. may be mentioned.

In addition to the above-mentioned compounds, the active radical generator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetraphenyl -1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound etc. may also be included.

The acid generator is, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate. Nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts such as diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate are included.

The photopolymerization initiators described above can be used individually or in combination of two or more types.

According to one embodiment of the present invention, the content of the photopolymerization initiator may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the total of the alkali-soluble resin and photopolymerizable compound included together. When the content of the photopolymerization initiator is contained within the above-mentioned range, the sensitivity of the self-luminous photosensitive resin composition containing it is improved, and the strength of the color conversion layer formed using it and the smoothness on the surface of the color conversion layer can be improved. there is.

If necessary, the self-luminous photosensitive resin composition of the present invention may further include a photopolymerization initiation auxiliary agent along with the above-described photopolymerization initiator. The photopolymerization initiation aid may be used to further promote polymerization of the photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator included.

The type of the photopolymerization initiation aid is not particularly limited in the present invention, and can be used without particular limitation as long as it is used as a photopolymerization initiation aid in the industry, for example, amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone compounds. etc. can be mentioned.

Examples of the amine-based compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethyl benzoate. Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(di Examples include ethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone, and among these, 4,4'-bis(diethylamino)benzophenone may be preferable.

Examples of the alkoxyanthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene, etc. can be mentioned.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chlorothioxanthone. -4-propoxythioxanthone, etc. can be mentioned.

The above-mentioned photopolymerization initiation aids can be used individually or in a mixture of two or more types, and commercially available ones can also be purchased and used.

Examples of the commercially available photopolymerization initiation aid include the brand name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.).

In this way, when a photopolymerization initiation aid is further included, its content may be 10 moles or less per 1 mole of the photopolymerization initiator included, and preferably 0.01 to 4 moles. When the photopolymerization initiation aid is included within the above-mentioned range, the sensitivity of the self-luminous photosensitive resin composition containing it can be further improved, and the productivity of the color conversion layer formed thereby can be further improved.

solvent

The type of the solvent is not particularly limited in the present invention, and organic solvents used as solvents in the art can be used without particular limitation.

The solvent includes, for example, 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, and diethylene glycol diethyl. Ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol monomethyl ether. Alkylene glycol alkyl ether acetates such as acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl Ketones such as ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, Ester, such as methyl 3-methoxypropionate, and cyclic ester, such as γ-butyrolactone, are mentioned. Among the above solvents, organic solvents with a boiling point of 100°C to 200°C can be preferably used in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate, or 3-ethoxypropionate. -Esters such as methyl methoxypropionate are included, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. Examples include, but are not limited to. The above-mentioned solvents can be used individually or in mixture of two or more types.

The content of the solvent may be 60 to 90% by weight, preferably 70 to 85% by weight, based on the entire self-luminous photosensitive resin composition. When the content of the solvent is within the above-mentioned range, the applicability can be improved when applied with a coating device such as a roll coater, spin coater, slat and spin coater, slit coater (also called die coater), and inkjet.

additive

The type of the additive is determined as needed and is not particularly limited in the present invention.

The additives include, for example, fillers, other polymer compounds, dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents.

The filler may include, for example, glass, silica, alumina, etc.

The other polymer compounds include, for example, curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can be mentioned.

As the dispersant, for example, a commercially available surfactant can be used. Examples of the surfactant include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. In addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl phethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethylene imines, etc. Product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), and MEGAFAC (Dainippon Ink). Manufactured by Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.) ), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), etc.

The adhesion promoter is, 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-mercaptopropyl Trimethoxysilane, etc. can be mentioned.

Examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

The ultraviolet absorber specifically includes, for example, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothiriazole, alkoxybenzophenone, etc.

Examples of the anti-agglomeration agent include sodium polyacrylate.

The method for producing the self-luminous photosensitive resin composition of the present invention can be produced by a method commonly used in the art, and is not particularly limited in the present invention, but can be produced by, for example, the following method.

The colorant including the fluorescent dye of the present invention is dissolved by mixing with a solvent in advance, and at this time, part or all of the dispersant and alkali-soluble resin may be mixed together, if necessary. A self-luminous photosensitive resin composition can be obtained by adding the remainder of the alkali-soluble resin, photopolymerizable chemical, and photopolymerization initiator to the dispersion thus obtained, and further adding additives and additional solvents to reach a predetermined concentration, if necessary.

< color conversion layer >

The color conversion layer according to another aspect of the present invention includes a cured product of the self-luminous photosensitive resin composition.

The cured product may be a photocured product cured by irradiating light to the self-luminescent photosensitive resin composition, and in this case, the curing method of the photocured product may be a conventional method used in the art. For example, light can be irradiated onto the entire surface of the film coated with the self-luminous photosensitive resin composition using a light source such as a high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, excimer lamp, laser light, lens, mirror, etc. The photocurable composition can also be irradiated while scanning the convergence light obtained using . In addition, when using a mask having a light transmitting portion of a predetermined pattern, non-converged light can be irradiated to the composition through the mask, or a light guide member made by bundling a plurality of optical fibers can be used, and in this light guide member, optical fibers corresponding to a predetermined pattern can be used. A cured product can be formed by irradiating light to the photosensitive resin composition.

Figure 1 illustrates a color filter according to an embodiment of the present invention, which will be described in more detail with reference to this.

In the case of a typical image display device including a color conversion layer 20, color is realized by light emitted from the light source 10 passing through the color conversion layer 20. In this process, a portion of the light is transmitted through the color conversion layer. (20) This may cause a problem of reduced light efficiency due to absorption.

However, the color conversion layer 20 of the present invention includes a cured product of a self-luminous photosensitive resin composition containing two or more types of red fluorescent dyes, so that when applied to an image display device, it is emitted from the light source 10 of the image display device. One type of fluorescent dye emits energy by the light (wavelength), and the other type of fluorescent dye absorbs the emitted energy to express fluorescence, resulting in higher fluorescence efficiency than when containing only one type of fluorescent dye. There are excellent advantages (see Figure 1).

The thickness of the color conversion layer 20 may be, for example, 0.5 μm to 500 μm, but is not limited thereto and may be adjusted differently depending on the desired fluorescence efficiency.

<Color filter>

The color filter according to another aspect of the present invention has the advantage of being able to reproduce high colors by including the color conversion layer.

Figure 1 illustrates a color filter according to an embodiment of the present invention, which will be described in more detail with reference to this.

The color filter may include the color conversion layer 20 on top of the light source 10, and may further include a substrate and a pattern layer 30 on the color conversion layer 20. At this time, the substrate may be the substrate of the color conversion layer 20 itself, or may be any area where the color conversion layer is located in a display device, etc., and is not particularly limited.

The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may include, but is limited to, polyethersulfone (PES) or polycarbonate (PC). It doesn't work.

The pattern layer 30 can be formed using a conventional photosensitive resin composition used in the industry using a conventional method, for example, by applying the photosensitive resin composition, exposing, developing, and thermally curing it in a predetermined pattern. can be formed.

The pattern layer 30 may include, for example, a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. When light is irradiated, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

When applying the pattern layer 30 to an image display device, the light emitted from the light source 10 is not particularly limited, but a light source that emits blue light can be used in terms of better color reproduction.

The pattern layer 30 may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer 30 may further include a transparent pattern layer that does not contain quantum dot particles.

In the case where only the pattern layer 30 of two colors is provided, the light source 10 that emits light with a wavelength representing the remaining colors not included can be used. For example, when it includes a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer emits blue light as it is and appears blue.

The color filter including the substrate and pattern layer 30 as described above may further include partition walls formed between each pattern, and may further include a black matrix. In addition, the color conversion layer 20 may further include a protective film formed on the pattern layer 30.

<Image display device>

An image display device according to another aspect of the present invention has the advantage of being able to reproduce high colors by including the color filter described above.

The image display device specifically includes a liquid crystal display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for game consoles, a display device for portable terminals such as mobile phones, and a display device for digital cameras. display devices, such as display devices for car navigation, etc., and color display devices may be particularly suitable.

The image display device may include other components that are typically included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention, but this is not limited to the present invention. No.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the attached patent claims. In the following examples and comparative examples, “%” and “part” indicating content are based on weight, unless otherwise specified.

Synthesis example One: Perylenebisimide series synthesis of compounds

Synthesis example 1-1: Intermediate compound ( INT ) synthesis of

1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (0.11 mol) and 2,6-diisopropylaniline (0.44 mol) were added to 1 L of propionic acid, then heated and incubated at 140°C for 5 hours. The response was maintained. The reaction solution prepared in this way was cooled to room temperature, and the precipitate was filtered under reduced pressure and washed with methanol. The filtered filtrate was dispersed in water and maintained for 30 minutes and then filtered under reduced pressure. It was again dispersed in methanol and maintained for 30 minutes and then filtered under reduced pressure. After drying the filtered product, an intermediate compound (INT) was obtained with a yield of 80.5%. The reaction expected to occur when this intermediate compound is synthesized is shown in [Reaction Formula 1] below.

[Scheme 1]

MS (Mass Spectrometry) analysis was performed on the formed intermediate compound (INT) using a MALDI-TOF measurement device. As a result, it was confirmed that the molecular weight was 848.16.

Synthesis example 1-2: [Formula 6- 2] Synthesis of the indicated compounds

Potassium carbonate (0.04 mol) was added to the solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Synthesis Example 1-1, and the temperature was raised to 120°C. A solution of 2,4-dimethylphenol (0.32 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution prepared in this way at 120°C for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-cumylphenol (0.32 mol) and potassium carbonate (0.16 mol) were added, and stirring was maintained for 4 hours. The reaction solution prepared in this way was cooled to room temperature and discharged into 3L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtered filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound represented by [Formula 6-2] with a yield of 36.0%. did. The reaction expected to occur when the compound represented by [Formula 6-2] is synthesized is as shown in [Reaction Formula 2] below, and the molecular weight measured using a MALDI-TOF measuring device was 1281.57.

[Scheme 2]

Synthesis example 2: Synthesis of alkali-soluble resin (B)

A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and 118.0 g of vinyl toluene were added. (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and mixed with stirring, and 6 g of n-dodecanethiol was added as a chain transfer agent dropping tank. , 24 g of PGMEA was added and mixed with stirring. Afterwards, 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, the monomer and chain transfer agent were started dropwise from the dropping funnel. Dropping was carried out for 2 hours while maintaining the temperature at 90°C. After 1 hour, the temperature was raised to 110°C and maintained for 3 hours, and then a gas introduction tube was introduced to mix oxygen/nitrogen = 5/95 (v/v). Bubbling of gas started. Next, 28.4 g of glycidyl methacrylate (0.10 mol, 33 mol% based on the carboxyl group of acrylic acid used in this reaction), 0.4 g of 2,2'-methylenebis(4-methyl-6-t-butylphenol), 0.8 g of triethylamine was added into the flask, reaction was continued at 110°C for 8 hours, and Resin B with a solid acid value of 70 mgKOH/g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3. At this time, the GPC measurement conditions were as follows.

[GPC measurement conditions]

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Injection volume: 50 ㎕

Detector: RI

Measured sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as molecular weight distribution (Mw/Mn).

Example and Comparative example : self-luminous Preparation of photosensitive resin composition

A self-luminous photosensitive resin composition was prepared by mixing each of the components listed in Table 1 below in the amounts listed.

(Unit: weight%) Example Comparative example One One 2 3 4 Fluorescent dye Dye 1 (Yellow) - - - 0.7 - Dye 2 (Green) - - - - 0.7 Dye 3 (Red 1) 0.7 One - - - Dye 4 (Red 2) 0.3 One 0.3 0.3 Alkali soluble resin (B) 8.5 8.5 8.5 8.5 8.5 Photopolymerizable compound (C) 5.5 5.5 5.5 5.5 5.5 photopolymerization initiator D-1 0.83 0.83 0.83 0.83 0.83 D-2 0.33 0.33 0.33 0.33 0.33 Solvent (E) remaining amount remaining amount remaining amount remaining amount remaining amount Dye 1: Lumogen F (Y083, manufactured by BASF)
Dye 2: Coumarin 153
Dye 3: Lumogen F305 red (compound of formula 5)
Dye 4: Red dye prepared in Synthesis Example 1-2 (compound of Chemical Formula 6-2)
B: Alkali-soluble resin of Synthesis Example 2
C: Dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.)
D-1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one
(Irgacure 369; manufactured by Ciba Specialty Chemical)
D-2: 4,4'-di(N,N'-dimethylamino)-benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
E: propylene glycol monomethyl ether acetate

Manufacturing example: Manufacturing of color conversion layer

A color filter was manufactured using the self-luminous photosensitive resin composition prepared in each of the above examples and comparative examples. That is, each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100°C for 3 minutes to form a thin film. Then, ultraviolet rays were irradiated onto the thin film. At this time, the ultraviolet light source was irradiated with an exposure dose of 40 mJ/cm2 (365 nm) under an atmospheric atmosphere using an ultra-high pressure mercury lamp (product name: USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The ultraviolet irradiated thin film was developed in a KOH aqueous developing solution of pH 12.5 using a spray developer for 60 seconds and then heated in a heating oven at 230°C for 20 minutes to prepare a pattern. The film thickness of the color conversion layer pattern prepared above was 3.0 μm.

Experimental Example 1. Measurement of luminescence intensity

For each color conversion layer prepared in the above production example, the luminescence intensity for each color conversion layer was measured using a quantum efficiency meter (QE-1000, manufactured by Otsuka Corporation), and the results are listed in Table 2 below. did. At this time, it can be judged that the higher the measured luminescence intensity, the better the luminance characteristics.

Experimental Example 2. Heat resistance evaluation

The heat resistance of each color conversion layer prepared in the above production example was evaluated by comparing the color change before and after heating for 120 minutes at 230°C. At this time, the following equation 1 used represents the color change in a three-dimensional colorimeter defined by L*, a*, and b*. (Japanese Color Society edition, new edition Color Science Handbook (Showa 60) p. 266).

[Equation 1]

△Eab={(△L) ² +(△a) ² +(△b) ² } ^1/2

<Evaluation criteria>

○: △Eab is less than 2

×: △Eab is 2 or more

Experimental Example 3. Lightfastness evaluation

An ultraviolet cut filter (COLORED, OPTICAL, GLASS, L38; manufactured by Hoya; blocks light below 380 nm) was placed on each color conversion layer prepared in the above production example, and a light fastness tester (Santest CPS+: manufactured by Toyo Seiki) was used. , irradiated with xenon lamp light for 48 hours. The color change before and after irradiation was compared and evaluated. The mathematical equations and evaluation criteria used at this time were the same as those for the heat resistance evaluation.

Luminous intensity (λmax: 610) Heat resistance evaluation Lightfastness evaluation Example 1 4500 ○ ○ Comparative Example 1 4000 ○ ○ Comparative Example 2 3000 ○ ○ Comparative Example 3 5600 × × Comparative Example 4 6000 × ×

Referring to Table 2 above, when two different types of red fluorescent dyes are included as presented in the present invention (Example 1), and when only one type of red fluorescent dye is included (Comparative Examples 1 and 2) It was confirmed that the luminous intensity was superior and reliability such as heat resistance and light resistance was excellent. In addition, it was confirmed that reliability, such as heat resistance or light resistance, was superior to that in the case where a green fluorescent dye or a yellow fluorescent dye was further included (Comparative Examples 3 and 4).

10: light source
20: Color conversion layer
30: Pixel unit

Claims (16)

Contains a colorant containing two or more types of red fluorescent dyes,
A self-luminous photosensitive resin composition, wherein the colorant does not contain a yellow fluorescent dye. According to paragraph 1,
A self-luminous photosensitive resin composition, wherein the colorant does not contain a green fluorescent dye. According to paragraph 1,
The red fluorescent dye includes a first fluorescent dye and a second fluorescent dye, and is self-luminous, characterized in that part or all of the emission wavelength region of the first fluorescent dye and the absorption wavelength region of the second fluorescent dye overlap. Photosensitive resin composition. According to paragraph 3,
A self-luminous photosensitive resin composition, characterized in that the emission wavelength range of the first fluorescent dye is 500 to 640 nm, and the absorption wavelength range of the second fluorescent dye is 570 to 630 nm. According to paragraph 3,
The first fluorescent dye is a self-luminescent photosensitive resin composition, characterized in that it includes at least one selected from the group consisting of a dipyromethene-based compound, a rhodamine-based compound, a dicyanomethylene-based compound, and a perylenediimide-based compound: According to paragraph 4,
The second fluorescent dye is a self-luminous photosensitive resin composition, characterized in that it contains a compound represented by the following formula (6):
[Formula 6]

(In Formula 6 above,
R ₂₃ and R ₂₄ are each independently, 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl,
R ₂₅ to R ₂₇ are each independently hydrogen, a C1 to C10 straight or branched alkyl group, a C6 to C18 aryl group, a C7 to C18 arylalkyl group, a C1 to C18 alkoxy group, or a complex group with 1 to 30 atoms. It is a ventilation or halogen group,
x, y, z are integers from 1 to 5,
When x, y, and z are 2 or more, additional substituents R ₂₅ to R ₂₇ may be the same or different from each other). According to clause 5,
The dipyromethene-based compound is a self-luminous photosensitive resin composition, characterized in that it includes a compound represented by the following formula (1):
[Formula 1]

(In Formula 1 above,
R ₁ and R ₂ are each independently hydrogen, an alkyl group, a cycloalkyl group, an arylalkyl group, an alkylaryl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, an alkoxy group, an alkoxyaryl group, an alkylthio group, Aryl ether group, arylthioether group, aryl group, haloaryl group, heterocyclic group, halogen group, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, It is an amino group, nitro group, silyl group, or siloxanyl, or is connected to an adjacent substituent to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon or hetero ring,
Wherein L is hydrogen, alkyl group, cycloalkyl group, arylalkyl group, alkylaryl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkoxyaryl group, alkylthio group, arylether group, arylthioether group, aryl group, haloaryl group, heterocyclic group, halogen group, haloalkyl group, haloalkenyl group, haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group. or siloxanyl, or is connected to an adjacent substituent to form a substituted or unsubstituted aromatic or aliphatic hydrocarbon or hetero ring;
where m is an integer from 1 to 3,
M is the m-valent metal atom, and is boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc or platinum,
R ₃ to R ₇ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an amine group, or a substituted or unsubstituted arylalkenyl group, and the substituted alkyl group is substituted with a halogen atom, The substituted aryl group is substituted with a hydroxy group, an alkyl group, or an alkoxy group, and the substituted arylalkenyl group is substituted with an alkoxy group). According to clause 5,
The rhodamine-based compound is a self-luminous photosensitive resin composition, characterized in that it includes a compound represented by the following formula (2):
[Formula 2]

(In Formula 2 above,
R ₈ and R ₉ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,
R ₁₀ to R ₁₁ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,
R ₁₂ to R ₁₃ are each independently hydrogen, deuterium, COO-, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group). According to clause 5,
The dicyanomethylene-based compound is a self-luminous photosensitive resin composition, characterized in that it includes a compound represented by the following formula (3):
[Formula 3]

(In Formula 3 above,
R ₁₄ and R ₁₅ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,
R ₁₆ is hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group). According to clause 5,
The perylenediimide-based compound is a self-luminous photosensitive resin composition, characterized in that it includes a compound represented by the following formula (4):
[Formula 4]

(In Formula 4 above,
R ₁₇ and R ₁₈ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group,
R ₁₉ to R ₂₂ are each independently hydrogen, deuterium, an alkyl group, an alkoxy group, an aryl group, or an aryloxy group). According to paragraph 3,
A self-luminous photosensitive resin composition, characterized in that the weight ratio of the first fluorescent dye to the second fluorescent dye is 99:1 to 1:99. According to paragraph 1,
A self-luminous photosensitive resin composition, characterized in that the colorant is contained in an amount of 0.01 to 30% by weight based on the total solid content in the self-luminous photosensitive resin composition. According to paragraph 1,
The self-luminous photosensitive resin composition further comprises one or more selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive. A color conversion layer comprising a cured product of the self-luminous photosensitive resin composition of any one of claims 1 to 13. A color filter comprising the color conversion layer of claim 14. An image display device comprising the color filter of claim 15.