KR20210095313A - Self emission type photosensitive resin composition, color filter comprising color conversion layer using the same and display device - Google Patents

Abstract

The present invention relates to a spontaneous photosensitive resin composition which comprises: a hindered amine light stabilizer (HALs) whose base constant (pKb) is 5 to 10; a fluorescent pigment comprising a perylene bisimide-based compound; a binding agent resin; a photo-polymerizable compound; a photo-polymerization initiator; and a solvent, thereby having excellent fluorescent efficiency, excellent reliability such as heat resistance or light resistance, and high sensitivity.

Description

Self-luminous photosensitive resin composition, color filter and image display device comprising a color conversion layer prepared therefrom

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

Recently, the display industry has undergone a rapid change from CRT to flat panel displays represented by PDP, OLED, and LCD. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding. However, the LCD requires a separate backlight unit due to the absence of its own light emitting device.

A CCFL (Cold Cathode Fluorescent Lamp) was used as a light source of a general backlight unit. However, a backlight unit using a CCFL consumes a considerable amount of power because power is always applied to the CCFL, and has a color gamut of about 70% compared to a CRT, and environmental pollution problems due to the addition of mercury are pointed out as disadvantages. As an alternative to solve the above problems, research on a backlight unit using a Light Emitting Diode (LED) is being actively conducted. When an LED is used as a backlight unit, it can exceed 100% of the NTSC (National Television System Committee) color gamut specification to provide more vivid picture quality to consumers.

In addition, in the same industry, efforts have been made to improve the light efficiency by changing the material and structure of the color filter and the LCD panel to improve the efficiency of the backlight light source [refer to Korean Patent Application Laid-Open No. 10-2012-0048218].

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

This low color reproducibility problem can be improved by increasing the light efficiency of the color filter, and a method of increasing the thickness of the color filter or introducing a color conversion layer (or light conversion layer) in lamination or close proximity thereto is proposed. there is.

However, conventional dyes or pigments are used for the color conversion layer, and it is difficult to expect improvement in light efficiency only with these dyes and pigments, and a problem of lowering luminance occurs. Accordingly, a method of using a fluorescent material for the color conversion layer has been proposed [refer to Korean Patent Application Laid-Open No. 10-2016-0112479]. Accordingly, there is a demand for development of a self-luminous photosensitive resin composition capable of improving the fluorescence efficiency of the color conversion layer.

Republic of Korea Patent Publication No. 10-2012-0048218 (2012.05.15) Republic of Korea Patent Publication No. 10-2016-0112479 (2016.09.28)

The present invention is to solve the above problems, and includes a self-luminous photosensitive resin composition having excellent fluorescence efficiency and capable of producing a color conversion layer having high sensitivity, high efficiency or high reliability, and a color conversion layer prepared therefrom An object of the present invention is to provide a color filter and an image display device.

The self-luminous photosensitive resin composition of the present invention for achieving the above object includes a hindered amine-based light stabilizer having a base constant of 5 to 10; a fluorescent dye containing a perylene bisimide-based compound; binder resin; photopolymerizable compounds; photoinitiator; and solvents.

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

The color filter of the present invention includes the color conversion layer.

The image display apparatus of the present invention includes the color filter.

The self-luminous photosensitive resin composition of the present invention has advantages of excellent fluorescence efficiency, excellent reliability such as heat resistance or light resistance, and high sensitivity.

Since the color conversion layer of the present invention includes the cured product of the self-luminous photosensitive resin composition described above, it has excellent fluorescence efficiency, excellent color conversion characteristics, and excellent reliability such as heat resistance or light resistance.

Since the color filter of the present invention includes the above-described color conversion layer, high color reproduction is possible, and reliability such as heat resistance or light resistance is excellent.

The image display apparatus of the present invention has the same advantages as described above by including the color filter described above.

1 schematically illustrates an example of a color filter of the present invention.
2 is a view showing the results of the emission intensity test for the color conversion layer of an example of the present invention.

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

In the present invention, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

Each functional group described in the present invention may be independently substituted or unsubstituted, and the substitution is, for example, deuterium, a halogen group, a nitrile group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, It may mean substituted with one or more groups selected from the group consisting of an aryl group, a heteroaryl group, an arylamine group, a heterocyclic group, 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 linear or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 40, for example, 1 to 20. 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-methyl Heptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc. are mentioned. However, it is not limited thereto.

The number of carbon atoms of the 'cycloalkyl group' in the present invention is not particularly limited, but may be 3 to 30, for example 3 to 20. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

In the present invention, the 'alkenyl group' refers to an unsaturated hydrocarbon group having at least one carbon-carbon double bond in a straight or branched chain, and the number of carbon atoms is not particularly limited, but may be, for example, 2 to 30. Examples include, but are not limited to, ethenyl, vinyl, propenyl, allyl, isopropenyl, butenyl, isobutenyl, t-butenyl, n-pentenyl and n-hexenyl.

In the present invention, the 'cycloalkenyl 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' is a straight or branched chain, and refers to an 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, the 'aryl group' refers to a monovalent group of an aromatic hydrocarbon or an aromatic hydrocarbon derivative. The aromatic hydrocarbon refers to a compound in which pi electrons are completely conjugated and includes a planar ring, and the group derived from the 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 connected to each other. The number of carbon atoms in the aryl group is not particularly limited, but may be 6 to 60, preferably 6 to 40, unless otherwise specified. The aryl group may be monocyclic or polycyclic, and the monocyclic aryl group includes, for example, a phenyl group, a biphenyl group, a terphenyl group, and a quaterphenyl group, and the polycyclic aryl group includes, for example, a naphthyl group, an anthracenyl group , phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, tetracenyl group, chrysenyl group, fluorenyl group, indenyl group, acenaphthyl group, benzofluorenyl group, and the like. However, the present invention is not limited thereto.

In the present invention, the term 'heteroaryl group' refers to an aromatic or aliphatic heterocycle (also referred to as a heterocycle). Here, the aromatic heterocyclic ring is a group of an aromatic ring or a derivative of an aromatic ring, and means a group including at least one of N, O and S in the ring as a heteroatom. The derivative of the aromatic ring includes all structures in which an aromatic ring or an aliphatic ring is condensed on an aromatic ring. The number of carbon atoms in the heteroaryl group is not particularly limited, but may be 2 to 60, preferably 2 to 40, unless otherwise specified. For example, thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, 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, carbazolyl group, benz oxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, benzofuranyl group, dibenzofuranyl group, phenanthrolinyl group, thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenoxazinyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto. The heteroaryl group includes an aliphatic heteroaryl group and an aromatic heteroaryl group.

In the present invention, the 'alkoxy group' may include, for example, a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an iso-amyloxy group, a hexyloxy group, and the like. However, the present invention is not limited thereto.

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

In the present invention, the term 'heterocyclic group' refers to a cyclic chemical group having one or more atoms selected from N, O, and S and the remaining atom(s) is C atom(s). The 'heterocyclic group' is a single ring or a polycyclic ring. When the 'heterocyclic group' is aromatic, it is referred to as a 'heteroaryl group'. Heterocyclic groups may include 4-, 5-, 6-, 7- or 8-membered rings. Examples of the heterocyclic group include a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a morpholino group, a thiomorpholino group, a homopiperidinyl group, a chromanyl group, an isochromanyl group, a chromenyl group, a pyrrolyl group, a fura 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 group, pyranyl group, indolyl group, isoindolyl group, indazolyl group, purinyl group, indolizinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, pteridinyl group, quinolinyl group, benzoxa a zinyl group, a carbazolyl group, a phenazinyl group, a phenothiazinyl group, a phenanthridinyl group, etc. are mentioned.

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

< self-luminescence Photosensitive resin composition>

The self-luminous photosensitive resin composition according to an aspect of the present invention includes a hindered amine light stabilizer (HALs) having a base constant (PKb) of 5 to 10; a fluorescent dye containing a perylene bisimide-based compound; binder resin; photopolymerizable compounds; photoinitiator; And by including a solvent, there are advantages of excellent fluorescence efficiency, excellent reliability such as heat resistance or light resistance, and high sensitivity.

hindered amine light stabilizer ( Hindered Amine Light stabilizer : HALs )

The self-luminous photosensitive resin composition according to an embodiment of the present invention includes a hindered amine-based light stabilizer having a base constant (pKb) of 5 to 10, thereby improving reliability such as heat resistance or light resistance, and prevents yellowing There is an advantage in that it can be used, and the fluorescence efficiency is excellent, and the straightness of light can be improved.

The hindered amine-based light stabilizer may preferably have a base constant (pKb) of 5 to 7, and in this case, the luminous intensity may be further improved, thereby maximizing the effect of improving fluorescence efficiency.

The light stabilizer may be preferably a light stabilizer having a maximum absorption range of 350 nm or less (including j-line) when viewed in a wavelength range. An optical stabilizer having a maximum absorption region exceeding 350 nm may weaken the irradiation intensity of i-rays. The light stabilizer having a maximum absorption region at 350 nm or less may include, for example, a benzophenone derivative and a triazine derivative, but is not limited thereto.

As the hindered amine-based light stabilizer, any hindered amine-based light stabilizer used in the art may be used without particular limitation as long as it satisfies the above base constant range, but according to an embodiment of the present invention, the hindered amine-based light stabilizer The stabilizer may include a compound having the structure of Formula 1 in its molecular structure, and as such, when the hindered amine-based light stabilizer includes a compound containing the structure of Formula 1, the reliability of heat resistance or light resistance is high. It can be further improved, the occurrence of a yellowing phenomenon can be prevented, the fluorescence efficiency is more excellent, and there is an advantage that the straightness of the light can be further improved.

[Formula 1]

(In Formula 1,

R ₁ to R ₄ are each independently hydrogen, (C ₁ to C ₇ )alkyl group, hydroxy-(C ₁ to C ₇ )alkyl group, hydroxy-(C ₁ to C ₄ )alkyl group (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkoxy group or (C ₁ to C ₄ )alkoxycarbonyl group, or

R ₁ and R ₂ ; Or R ₃ and R ₄ ; each of which shares a C atom adjacent to each other (C ₃ to C ₇ ) A cycloalkyl group;

Ra or Rb is each independently hydrogen, (C ₁ to C ₄ )alkyl group, hydroxy-(C ₁ to C ₄ )alkyl group, (C ₆ to C ₁₀ )aryl group, (C ₆ to C ₁₀ )aryl- (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkyl-(C ₉ to C ₁₀ )aryl group, cyano group, (C ₁ to C ₄ )alkoxycarbonyl group, (C ₁ to C ₄ )alkoxycar Bornyl-(C ₁ to C ₄ )alkyl group, mono-(C ₁ to C ₄ )alkylcarbamoyl group, di-(C ₁ to C ₄ )alkylcarbamoyl group, mono-2-hydroxyethylcarbamoyl group, di-2-hydroxyethyl carbamoyl group, 1-hydroxy-2-hydroxymethyl-2-propyl carbamoyl group, 1,1-dihydroxymethyl-2-hydroxycarbamoyl group, amidino group, 2-imidazolyl group or -P=O(O-(C ₁ to C ₄ )alkyl) ₂ or

Ra and Rb are each bonded to each other as a divalent group to form a 5- to 8-membered aliphatic or aromatic heterocycle with or without at least one hetero atom selected from the group consisting of N, O and S,

X is C or O;

A is hydrogen, -C(R ₅ ) ₃ ,

Each of R ₅ is independently hydrogen, a substituted or unsubstituted, (C ₁ to C ₁₂ )alkyl group, (C ₅ to C ₁₂ )cycloalkyl group, (C ₆ to C ₁₂ )aryl group, cyano group, (C ₁ to C ₁₂ )alkenyl group, (C ₁ to C ₁₂ )carbonyl group, (C ₁ to C ₁₂ )ester group, -COR ₆ or -OC(=O)-CH ₂ CH ₂ -C(=O)- is,

Each of R ₆ is independently a (C ₁ to C ₈ )alkyl group, (C ₆ to C ₁₂ )aryl group, (C ₁ to C ₈ )alkoxy group, or —N(R ₇ ) ₂ ,

wherein R ₇ is each independently hydrogen or (C ₁ to C ₈ )alkyl group,

In A, aryl is each independently (C ₁ to C ₁₂ )alkyl group, halogen group, (C ₁ to C ₁₂ )alkoxy group, (C ₁ to C ₁₂ )alkylcarbonyl group, glycidyloxy group, -OH, -COOH Or -COO (C _{1 To} C ₁₂ ) It is unsubstituted or substituted with an alkyl group.)

Preferably, when any one of _{R 1} and R ₂ in Formula 1 _{is a (C 1} to C ₇ )alkyl group or a hydroxy-(C ₁ to C ₇ )alkyl group, the other one is hydroxy-(C ₁ to C ₄ ) It may be a (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkoxy group, or (C ₁ to C ₄ )alkoxycarbonyl group substituted or unsubstituted with an alkyl group, and R ₃ and R ₄ are each is independently hydrogen, or when any one of _{R 3} and R _{4 is a (C 1} to C ₇ )alkyl group or a hydroxy-(C ₁ to C ₇ )alkyl group, the other one is hydroxy-(C ₁ to C _{4 )} ) It may be a (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkoxy group, or (C ₁ to C ₄ )alkoxycarbonyl group substituted or unsubstituted with an alkyl group.

In Formula 1, aryl in A may be preferably phenyl.

More specifically, the hindered amine-based light stabilizer may include a copolymerizable piperidine-containing photostable compound such as 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and the like. The peridine-containing photostable compound may specifically include a structure of the following Chemical Formula 1-1, but is not limited thereto, and when such a compound is used, the reliability of the coating film is greatly improved without compromising storage stability or curability. There are benefits that can be improved.

[Formula 1-1]

(In Formula 1-1,

A, X and R ₁ to R ₄ are the same as defined in Formula 1 above,

n is an integer from 1 to 2.)

In addition, as a commercial product of the hindered amine light stabilizer, TINUVIN 144 (bis(1,2,2,6,6,-pentamethyl-4-piperidinyl){[3,5-bis(1,1) -Dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate (manufactured by BASF), TINUVIN 622 SF (manufactured by BASF), TINUVIN 123 (bis(2,2,6,6-tetramethyl-decane) 1-(octyloxy)-4-piperidinyl)ester, manufactured by BASF), etc., but are not limited thereto, and these may be used alone or in combination of two or more.

In addition, the self-luminous photosensitive resin composition of the present invention may further include a light stabilizer other than the light stabilizer of the above-mentioned conditions, but it is reliable to use only the light stabilizer that satisfies the above-mentioned conditions (base constant of 5 to 10). It may be preferable in terms of being able to further improve it. The light stabilizer that may be further included may include, for example, TINUVIN 770DF, TINUVIN 152, and the like, but is not limited thereto.

According to an embodiment of the present invention, the light stabilizer is 10 to 300 parts by weight, preferably 10 to 100 parts by weight, based on the solid content of the self-luminous photosensitive resin composition comprising the same, based on the total weight of the photopolymerization initiator, More preferably, it may be included in an amount of 20 to 50 parts by weight. When the content of the light stabilizer is included within the above range, high emission intensity of the self-luminous photosensitive resin composition can be expected. Due to the phenomenon, it may be difficult to expect high luminescence intensity.

fluorescent dye

The self-luminous photosensitive resin composition according to an embodiment of the present invention includes a fluorescent dye including a perylene bis-imide-based compound, and the perylene bis-imide-based compound may be a compound having a structure represented by the following Chemical Formula 2 . As such, when the perylene bisimide-based compound is included, there is an advantage in that fluorescence is increased and solubility in a solvent is improved. In addition, it exhibits good chemical, thermal and optical stability, which is advantageous for the application of the process.

[Formula 2]

(In Formula 2,

wherein R ₈ and R ₉ are each independently a (C ₆ to C ₂₀ )aryl group, (C ₃ to C ₁₀ )heterocyclic group, or (C ₁ to C ₁₀ )alkyl group,

wherein R ₁₀ to R ₁₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a (C ₁ to C ₁₀ )alkoxy group, or a functional group represented by the following Structural Formula 1.)

[Structural Formula 1]

(In Structural Formula 1,

Each of R ₁₄ is independently a (C ₁ to C ₁₀ )alkyl group, a halogen atom, a (C ₆ to C ₁₈ )aryl group, a (C ₇ to C ₁₈ )arylalkyl group, a hydroxyl group, a (C ₁ to C ₁₀ )alkoxy group , (C ₁ to C ₁₀ ) It is an ester group, an amine group, or a heterocyclic group having 3 to 30 atoms,

x is an integer from 1 to 5,

When any one or more of x is 2 or more, _{the functional groups of R 14} corresponding thereto may be the same or different from each other.)

The structure represented by Formula 2 may be, for example, a structure represented by Formula 2-1 below.

[Formula 2-1]

(In Formula 2-1,

R ⁸ to R ¹⁴ , Y and x are the same as defined in Formula 2 above.)

Formula 2 may also have, for example, a structure represented by Formula 2-2 below.

[Formula 2-2]

(In Formula 2-2,

R ₈ and R ₉ are each independently a (C ₁ to C ₁₀ ) aryl group unsubstituted or substituted with an alkyl group (C ₆ to C ₁₈ ),

R ₁₄ are each independently hydrogen, (C ₁ to C ₁₀ )alkyl group, (C ₆ to C ₁₈ )aryl group, (C ₇ to C ₁₈ )arylalkyl group, (C ₁ to C ₁₈ )alkoxy group, number of atoms 3 to 30, a heterocyclic group or a halogen group,

x is each independently an integer from 1 to 5,

When any one or more of x is 2 or more, _{the functional groups of R 14} corresponding thereto are the same or different from each other.)

According to one embodiment of the present invention, the perylene bisimide-based compound may have a structure represented by Formula 2-2. In this case, a substituent derived from the 4-cumylphenol group is introduced to reduce the steric hindrance effect thereof. Fluorescence can be further increased even at a high concentration through this, and solubility in a solvent can also be further increased. In addition, there is an advantage that the chemical, thermal and optical stability is further improved, which can be more advantageous for the application of the process.

According to an embodiment of the present invention, the compound of the structure represented by Formula 2-2 may be, for example, at least one selected from the group consisting of compounds represented by Formulas 2-3 to 2-11.

When the perylene bisimide-based compound includes at least one selected from the group consisting of compounds represented by Chemical Formulas 2-3 to 2-11, the fluorescence intensity can be further increased even at a high concentration, and the solubility in a solvent is improved. can increase In addition, it can exhibit better chemical, thermal and optical stability, so there is an advantage that can be more advantageous for the application of the process.

According to an embodiment of the present invention, the content of the fluorescent dye may be included in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight based on the total weight of the composition including the same. there is. When the fluorescent dye is included within the above range, it can have excellent luminescence intensity, and has good solubility and thus reliability can be further improved. If it is included below the above range, it may be difficult to expect an excellent luminous intensity effect, and if it exceeds the above range, reliability such as heat resistance or light resistance may be somewhat lowered, and problems such as discoloration or dissolution of dye may occur. may be

The self-luminous photosensitive resin composition of the present invention may further include a conventional fluorescent dye other than the above-described perylene bisimide-based compound if necessary, and the type thereof is not particularly limited in the present invention.

binder resin

The self-luminous photosensitive resin composition according to one aspect of the present invention includes a binder resin.

The binder resin generally has reactivity and alkali solubility under the action of light or heat, and acts as a dispersion medium for a coloring material (fluorescent dye or colorant, etc.). The binder resin contained in the self-luminous photosensitive resin composition of the present invention acts as a binder resin for the coloring material, and if it is a binder resin soluble in the alkaline developer used in the developing step for the production of the color conversion layer, the type is not particularly limited. can be used without

Examples of the binder resin include a carboxyl group-containing monomer and a copolymer of the monomer and another monomer copolymerizable with the monomer. Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule such as unsaturated tricarboxylic acids. can be heard Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid 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 thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), mono(2-acryloyloxyethyl phthalate), mono(2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, 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 Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylic Rate, methoxypropylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene 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 groups 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, a vinyl propionate, a vinyl butyrate, and a 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-hydroxyethylmethacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexyl maleimide; 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 having These monomers can be used individually or in mixture of 2 or more types, respectively. In particular, as another monomer copolymerizable with the carboxyl group-containing monomer, bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton are preferable because they tend to lower the relative dielectric constant. .

The acid value of the binder resin of the present invention is not particularly limited in the present invention, but may be preferably in the range of 20 to 200 (mgKOH/g). When 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 is increased, so that the pattern of the exposed portion remains at the time of development, which is preferable, so that the film remaining ratio can be improved. do. 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 obtained by titration using an aqueous potassium hydroxide solution.

In addition, the binder resin has a polystyrene equivalent weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (using GPC tetrahydrofuran as an elution solvent) of 3,000 to 200,000, preferably 5,000 to 100,000 binder resins may be preferred. When the molecular weight is in the above range, the hardness of the color conversion layer is improved, the remaining film rate can be excellent, the solubility of the non-exposed part in the developer can be further improved, 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 may be preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0, it is preferable because developability can be further improved.

The content of the binder resin may be usually 5 to 85% by weight, preferably 10 to 70% by weight based on the total solid content in the composition including the same. When the content of the binder resin is within the above range, the solubility in the developer is sufficient, so that it may be difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development. It is preferable because the omission property of the part can be improved.

photopolymerization compound

The self-luminous photosensitive resin composition according to an embodiment of the present invention includes a photopolymerizable compound.

The photopolymerizable compound is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrol money, etc. 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, and di and pentaerythritol hexa(meth)acrylate, but is not limited thereto, and these may be used alone or in combination of two or more. Among these, a polyfunctional monomer having a bifunctional or higher function can be preferably used.

The content of the photopolymerizable compound may be 5 to 50% by weight, preferably 7 to 45% by weight, based on the total solid content of the composition including the same. When the content of the photopolymerizable compound is included within the above range, the strength or smoothness of the pixel portion may be improved, which is preferable.

light curing initiator

The self-luminous photosensitive resin composition according to an aspect of the present invention includes a photopolymerization initiator.

The photopolymerization initiator may preferably contain an acetophenone-based compound. Examples of the acetophenone-based compound include 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-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1 -one oligomer etc. are mentioned, Preferably, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)butan-1-one etc. are mentioned.

In addition, the photopolymerization initiator may further include a photopolymerization initiator other than the acetophenone-based photopolymerization initiator. The photopolymerization initiator other than the acetophenone-based photopolymerization initiator may include, but is not limited to, an active radical generator, a sensitizer, an acid generator, and the like that generate active radicals by irradiating light. Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and a triazine-based compound. As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo isobutyl ether, etc. are mentioned, for example. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone etc. are mentioned. 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-(4-methoxystyryl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-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 etc. are mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used. The acid generator includes, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. In addition, as an active radical generator, some of the compounds generate an acid simultaneously with an active radical. For example, a triazine-based photopolymerization initiator may be used as an acid generator.

The content of the photoinitiator may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the total weight of the binder resin and the photopolymerizable compound included together based on the solid content. When the content of the photopolymerization initiator is included within the above range, the self-luminous photosensitive resin composition is highly sensitive, so that the strength of the pixel portion formed using the composition or smoothness on the surface of the pixel portion may be improved, which is preferable.

The self-luminous photosensitive resin composition of the present invention may further include a photopolymerization initiator adjuvant together with the above-described photopolymerization initiator.

The photopolymerization initiation adjuvant may be used together with a photoinitiator, and may be used to promote polymerization of a photopolymerizable compound whose polymerization is initiated by the photoinitiator. Examples of the photopolymerization initiation adjuvant include, but are not limited to, amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.

Examples of the amine compound 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 ethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone may be preferable. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene etc. are mentioned. As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone and the like may be mentioned, but is not limited thereto.

These photoinitiation adjuvants may be used individually or in combination of 2 or more types. Moreover, a commercially available thing can be used as a photoinitiation adjuvant, As a commercially available photoinitiation adjuvant, the brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

As such, when the photopolymerization initiator is further included, the amount used may be generally 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator included together. When the amount of the photopolymerization initiation adjuvant is included within the above range, the sensitivity of the self-luminous photosensitive resin composition including the same may be further improved, and the productivity of the color conversion layer formed using the composition may be further improved.

solvent

The self-luminous photosensitive resin composition according to an embodiment of the present invention includes a solvent.

The type of the solvent is not particularly limited in the present invention, and various organic solvents used in the field of the self-luminous photosensitive resin composition may be used. For example, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, di Diethylene glycol dialkyl ethers such as ethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene alkylene glycol alkyl ether acetates such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; 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-methyl Esters, such as methyl oxypropionate, cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned, These can be used individually or in mixture of 2 or more types, respectively.

Among the above solvents, an organic solvent having a boiling point of preferably 100°C to 200°C can be used in terms of applicability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid Esters such as ethyl or methyl 3-methoxypropionate can be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3-methyl methyl oxypropionate and the like can be used.

The content of the solvent may be 60 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the self-luminous photosensitive resin composition including the solvent. When the content of the solvent is within the above range, the coating property may be better when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), an inkjet, etc. there is.

coloring agent

The self-luminous photosensitive resin composition of the present invention may further include a colorant if necessary, in this case, the colorant may include at least one selected from the group consisting of an organic colorant or an inorganic colorant, and the organic colorant is an organic pigment. Or an organic dye may be used, and the inorganic colorant may include an inorganic pigment or an inorganic dye, but is not limited thereto. The colorant may be present in the form of a mill base. The organic pigment and/or organic dye may be a synthetic dye or a natural dye. The organic pigment is fine particles by rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment to the surface of the pigment using a polymer compound, etc., if necessary A chemical treatment or a washing treatment with an organic solvent or water to remove impurities may be performed. The inorganic pigment may be a metal oxide, a metal complex salt, an inorganic salt of barium sulfate (physical pigment), or the like. In this case, the layer having the main color of the mill base is the same as the pigment used in the conventional mill base.

The colorant may have a particle size of 3 to 150 nm, and when it falls within the above range, it may be advantageous to maintain a dispersed state in the liquid phase. More specifically, the organic colorant among the colorants may be preferable when the particle size is 20 to 100 nm. When the organic colorant satisfies the above range, it may be advantageous in terms of dispersion stability. This is because if the size is less than the above range, the surface area of the colorant is rapidly increased and dispersion stability may be reduced, and aggregation between the colorants may occur, and if the size exceeds the above range, the weight of the colorant may increase. Therefore, dispersion stability may be deteriorated and precipitation may occur. Among the colorants, the inorganic colorant may have a particle size of 3 to 20 nm. When the inorganic colorant has a size within the above range, it may be preferable in terms of increased storage stability due to excellent dispersibility.

additive

The self-luminous photosensitive resin composition of the present invention may further include additives other than the above-mentioned components, if necessary.

The additives may include, but are not limited to, fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors.

Specific examples of the filler include glass, silica, alumina, and the like. Specific examples of the other high molecular compounds include 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 As said pigment dispersant, commercially available surfactant can be used, For example, surfactant, such as silicone type, fluorine type, ester type, cationic type, anionic type, nonionic type, amphoteric type, etc. are mentioned. These may be used individually or in combination of 2 or more types, respectively. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, Polyethylenimines, etc., in addition to the trade names KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (manufactured by Dainippon Ink Chemical Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (SOLSPERSE) (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals Corporation), and PB 821 (manufactured by Ajinomoto Corporation). As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane etc. are mentioned. Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol. Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotyriazole and alkoxybenzophenone. Specific examples of the aggregation inhibitor include sodium polyacrylate. These can be used individually or in mixture of 2 or more types, respectively.

The self-luminous photosensitive resin composition of the present invention may be prepared by a method commonly known in the art, for example, may be prepared by the following method.

The fluorescent dye is previously mixed with a solvent and dissolved. In this case, if necessary, a colorant and a pigment dispersant may be further included. Moreover, some or all of binder resin may be mix|blended. In the dispersion (hereinafter, sometimes referred to as mill base) thus obtained, the remainder of the binder resin, a photopolymerizable compound and a photoinitiator, other components (additives, etc.) used as necessary, and an additional solvent are added to a predetermined concentration. Furthermore, the desired self-luminescence photosensitive resin composition can be obtained by adding.

< 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 described above.

When the color conversion layer is applied to an image display device, since it emits light by the light of the image display device light source, by including the cured product of the self-luminous photosensitive resin composition of the present invention, the dispersibility of the fluorescent dye becomes good and the fluorescence efficiency By this improvement, color reproducibility is more excellent, and since light is emitted in all directions by photoluminescence, not only a viewing angle is improved, but also reliability such as heat resistance or light resistance is improved.

More specifically, in a conventional image display device including the color conversion layer 20 , white light passes through the color conversion layer 20 to realize color, and in this process, a part of the light is absorbed by the color conversion layer 20 . Light efficiency may be reduced. However, in the case of including the color conversion layer 20 made of the self-luminous photosensitive resin composition of the present invention, the dispersibility of the fluorescent dye is excellent and the fluorescence retention is improved, thereby realizing superior light efficiency (see FIG. 1). .

The cured product may be a photocured material cured by irradiating light to the self-luminous photosensitive resin composition of the present invention. For example, a light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp may be used to irradiate light to the entire surface of the coating film coated with the self-luminous photosensitive resin composition, laser light or a lens, a mirror, etc. It is also possible to irradiate the photocurable composition while scanning the converged light etc. obtained using In addition, when a mask having a light transmitting portion having a predetermined pattern is used, a light guide member formed by irradiating unconverged light to the composition through the mask or bundling a plurality of optical fibers may be used, and the optical fiber corresponding to the predetermined pattern in the light guide member A cured product can be formed by irradiating light through the photosensitive resin composition.

The thickness of the color conversion layer is not particularly limited in the present invention, but may be, for example, 0.5 to 500 μm, preferably 0.5 to 100 μm, more preferably 1 to 10 μm, and most preferably 1 to 5 μm. there is. When the thickness of the color conversion layer is included within the above range, there is an advantage in having excellent light emission intensity.

<Color filter>

Since the color filter according to another aspect of the present invention includes the color conversion layer described above, it has excellent fluorescence efficiency and excellent reliability such as heat resistance or light resistance.

Referring to FIG. 1, the color filter includes a substrate and a pattern layer 30 formed on the upper portion of the substrate in addition to the color conversion layer 20 described above, wherein the substrate may be a substrate of the pattern layer 30 itself, Alternatively, it may be a portion where the pattern layer 30 is positioned on a display device, etc., and is not particularly limited in the present invention.

The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may include polyethersulfone (PES) or polycarbonate (PC), but is limited thereto. it's not going to be

The pattern layer 30 may be a layer formed by applying a self-luminous or colored photosensitive resin composition and then exposing, developing, and thermosetting in a predetermined pattern.

The pattern layer 30 formed of the self-luminous photosensitive resin composition may include 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.

In such a case, the light emitted from the light source 10 is not particularly limited when applied to an image display device, but a light source emitting blue light may be used in terms of superior color reproducibility.

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.

When only two types of color pattern layers are provided, a light source emitting light of a wavelength representing the remaining colors that is not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may 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 transmits the blue light as it is to display blue color.

The color filter including the substrate and the pattern layer 30 as described above may further include a barrier rib formed between each pattern, and may further include a black matrix. In addition, it may further include a protective layer formed on the pattern layer.

<Image display device>

An image display device according to another aspect of the present invention includes the above-described color filter, and thus has excellent reliability such as heat resistance or light resistance and excellent color reproducibility.

Specifically, the image display device includes a light emitting device such as a light source 10 (refer to FIG. 1), a light guide plate, and other components that can be included in an image display device, such as a liquid crystal display unit including a color filter according to the present invention. can be, and the present invention is not limited thereto.

The image display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (including an organic EL display device, OLED and QLED), a liquid crystal projector, a game

display devices for use, display devices for portable terminals such as mobile phones, display devices for digital cameras, display devices for vehicle navigation, and the like, but are not limited thereto.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are only illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Synthesis example One: Perylene bis Synthesis of imide compounds

Synthesis example 1-1: intermediate compound ( INT ) synthesis

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, and then the temperature was raised to 140° C. for 5 hours. The reaction was maintained to prepare a reaction solution. The reaction solution thus prepared was cooled to room temperature, the precipitate was filtered under reduced pressure, and washed with methanol. The filtered filtrate was dispersed in water and maintained for 30 minutes, filtered under reduced pressure, dispersed again in methanol, maintained for 30 minutes, and then filtered under reduced pressure. After drying the filtered filtrate, the intermediate compound (INT) was obtained in a yield of 80.5%. The reaction expected to occur when the intermediate compound is synthesized as described above is shown in [Scheme 1] below.

[Scheme 1]

MS (Mass Spectrometric) was measured for the intermediate compound thus formed using a MALDI-TOF measuring device. As a result, it was confirmed that the molecular weight was 848.16.

Synthesis example 1-2: [Formula 2- 4] of compound synthesis

Potassium carbonate (0.04 mol) was added to a solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 1-1, and then the temperature was raised to 120°C. To the thus prepared reaction solution, a solution obtained by dissolving 2,4-dimethylphenol (0.32 mol) in N-methylpyrrolidone (88.7 g) was added 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 thus prepared was cooled to room temperature and discharged into 3 L 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 of [Formula 2-4] in a yield of 36.0%. As such, the reaction expected to occur when the compound of [Formula 2-4] is synthesized is as shown in [Scheme 2] below, and the MS measured using the MALDI-TOF measuring device was 1281.57.

[Scheme 2]

Synthesis example 1-3: [Formula 2- 8] of compound synthesis

Potassium carbonate (0.04 mol) was added to a solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Synthesis Example 1-1, and then the temperature was raised to 120°C. To the thus prepared reaction solution, a solution obtained by dissolving 4-butylphenol (0.16 mol) in N-methylpyrrolidone (88.7 g) was added at 120° C. for 2 hours. After maintaining the reaction at the same temperature for 1 hour, 4-cumylphenol (0.04 mol) and potassium carbonate (0.16 mol) were added, and stirring was maintained for 4 hours. The reaction solution thus prepared was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtered filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of [Formula 2-8] in a yield of 40.4%. The reaction expected to occur when the compound of [Formula 2-8] is synthesized is as shown in [Scheme 3] below, and the MS measured using the MALDI-TOF measuring device was 1364.69.

[Scheme 3]

Synthesis example 1-3: [Formula 2- 11] of compound synthesis

Potassium carbonate (0.04 mol) was added to a solution of INT (0.04 mol) and N-methylpyrrolidone (266.1 g) prepared in Synthesis Example 1-1, and then the temperature was raised to 120°C. To the thus prepared reaction solution, a solution obtained by dissolving 4-butylphenol (0.32 mol) in N-methylpyrrolidone (88.7 g) was added 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 thus prepared was cooled to room temperature and discharged into 3 L of distilled water. The resulting purple precipitate was filtered under reduced pressure and washed with methanol. The filtered filtrate was redissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized from MeOH to obtain the compound of [Formula 2-11] in a yield of 36.0%. As such, the reaction expected to occur when the compound of [Formula 2-11] is synthesized is as follows [Scheme 4], and the MS measured using the MALDI-TOF measuring device was 1426.7.

[Scheme 4]

Synthesis example 2: Synthesis of binder resin

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g of vinyltoluene were prepared as a monomer dropping funnel. (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added, prepared by stirring and mixing, and 6 g of n-dodecanthiol as a chain transfer agent dropping tank , PGMEA 24g was put and stirred and mixed, was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was substituted from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dripping proceeded for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 3 hours, and then a gas introduction tube was introduced to mix oxygen/nitrogen = 5/95 (v/v). Bubbling of gas was 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)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were put into the flask, and the reaction was continued at 110° C. for 8 hours to obtain a binder resin having a solid content acid value of 70 mgKOH/g. The polystyrene equivalent weight average molecular weight 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 Toso Co., Ltd.)

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

Column temperature: 40°C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass % (solvent = tetrahydrofuran)

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

Ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw/Mn).

Example and comparative example : self-luminescence Preparation of photosensitive resin composition

A self-luminous photosensitive resin composition was prepared in the configuration shown in Table 1 below.

(Unit:% by weight) Fluorescent dye (A) binder resin photopolymerizable compound photopolymerization initiator solvent light stabilizer
(Hindered Amine Light stabilizer: HALs) A1 A2 A3 A4 B C D E F1 F2 F3 F4 F5 Example One 0.4 - - - 9.24 9.24 0.74 80.02 0.36 - - - - 2 - 0.4 - - 9.24 9.24 0.74 80.02 0.36 - - - - 3 - - 0.4 - 9.24 9.24 0.74 80.02 0.36 - - - - 4 0.4 - - - 9.24 9.24 0.74 80.02 - 0.36 - - - 5 0.4 - - - 9.24 9.24 0.74 80.02 - - 0.36 - - 6 0.4 - - - 9.24 9.24 0.74 80.02 0.18 0.18 - - - 7 0.4 - - - 9.24 9.24 0.74 80.02 0.18 - - 0.18 - 8 0.4 - - - 9.24 9.24 0.74 80.02 0.18 - - - 0.18 9 0.4 - - - 9.33 9.33 0.74 80.02 0.18 - - - - 10 0.4 - - - 9.12 9.12 0.74 80.02 0.60 - - - - 11 0.4 - - - 9.00 9.00 0.74 80.02 0.84 - - - - 12 0.4 - - - 8.67 8.67 0.74 80.02 1.50 - - - - comparative example One 0.4 - - - 9.42 9.42 0.74 80.02 - - - - - 2 0.4 - - - 9.24 9.24 0.74 80.02 - - - 0.36 - 3 0.4 - - - 9.24 9.24 0.74 80.02 - - - - 0.36 4 - - - 0.4 9.24 9.24 0.74 80.02 0.36 - - - - A1: Compound of Formula 2-4 (red dye)
A2: Compound of Formula 2-8 (red dye)
A3: Compound of Formula 2-11 (red dye)
A4: Coumarin 6 (manufactured by Sigma-Aldrich)
B: binder resin of Synthesis Example 2
C: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)
E: propylene glycol monomethyl ether acetate
F1: TINUVIN 144 (pKb 5-7) (manufactured by BASF)
F2: TINUVIN 622 SF (pKb 7~8) (manufactured by BASF)
F3: TINUVIN 123 (pKb 8-10) (manufactured by BASF)
F4: TINUVIN 770 DF (pKb 4 to 4.8) (manufactured by BASF)
F5: TINUVIN 152 (pKb 12) (manufactured by BASF)

manufacturing example : color conversion layer manufacturing

A color conversion layer was prepared using each of the self-luminous photosensitive resin compositions prepared in Examples and Comparative Examples. That is, each of the self-luminous photosensitive resin compositions was applied on a glass substrate by spin coating, 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 on the thin film. At this time, the ultraviolet light source was irradiated with an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Denki Co., Ltd. at an exposure dose (365 nm) of 40 mJ/cm 2 in an atmospheric atmosphere, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed in a KOH aqueous solution developing solution having a pH of 12.5 for 60 seconds using a spray developer, and then heated in a heating oven at 220° C. for 20 minutes to prepare a pattern. The film thickness of each color conversion layer prepared above was 3.0㎛.

Experimental example 1: Luminescence intensity ( Intensity ) measurement

Each of the color conversion layers prepared in Preparation Example was measured for light emission intensity on each coated substrate using a quantum efficiency measuring instrument (QE-1000, manufactured by Otsuka Corporation). For each color conversion layer, the maximum emission wavelength (λ _max ) The light emission intensity was measured and the results are shown in Table 2 and FIG. 2 below.

λ _max Luminescence intensity
(Intensity) Example 1 600 11158 Example 2 600 11012 Example 3 600 10953 Example 4 600 10424 Example 5 600 10865 Example 6 600 10718 Example 7 600 10571 Example 8 600 10277 Example 9 600 11012 Example 10 600 10248 Example 11 600 10057 Example 12 600 9984 Comparative Example 1 600 8516 Comparative Example 2 600 7635 Comparative Example 3 600 6313 Comparative Example 4 600 8432

Referring to Table 2, in the case of Examples 1 to 12 satisfying all the conditions of the present invention, it was confirmed that the luminescence intensity was superior to those of Comparative Examples 1 to 4 which did not satisfy any one of the conditions of the present invention.

Experimental example 2: Heat resistance evaluation

After each color conversion layer prepared in Preparation Example was left in an oven at 200° C. for 4 hours, the chromaticity before and after leaving was calculated using Equation 1 below, and the calculated values before and after leaving The difference was evaluated according to the following evaluation criteria, and the results are shown in Table 3 below. At this time, it is judged that the heat resistance is excellent, so that the change value of color is small.

[Equation 1]

^{△ Eab * = [(△ L} *) 2 + (△ a *) 2 + (△ b *) 2] 1/2

(In the equation 1, △ L ^*, a ^* △, △ b ^* three-dimensional means a color change in the colorimetric Japan Color Institute piece, sinpyeon Color Science Handbook (1985 each) p.266)

<Evaluation criteria>

○: 0 < △Eab ^* < 1.5

△: 1.5 ≤ △Eab ^* < 2.0

×: 2.0 ≤ △Eab ^*

Experimental example 3: light fastness evaluation

After leaving each color conversion layer prepared in Preparation Example under CCFL backlight for 240 hours, the chromaticity before and after leaving was calculated using Equation 1, respectively, and the difference between the calculated values before and after leaving It was evaluated by the same evaluation criteria as in Experimental Example 2, and the results are shown in Table 3 below. At this time, it is determined that the light resistance is excellent as the change value of the color is small.

heat resistance light fastness Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Example 4 ○ ○ Example 5 ○ ○ Example 6 ○ ○ Example 7 ○ ○ Example 8 ○ ○ Example 9 ○ ○ Example 10 ○ ○ Example 11 ○ ○ Example 12 ○ ○ Comparative Example 1 △ × Comparative Example 2 × × Comparative Example 3 × × Comparative Example 4 × △

Referring to Table 3, in the case of Examples 1 to 12, which satisfy all the conditions presented in the present invention, heat resistance and light resistance are higher than those of Comparative Examples 1 to 4, which do not satisfy any one of the conditions presented in the present invention. It was confirmed that it was excellent.

10: light source
20: color conversion layer
30: pattern layer

Claims (9)

a hindered amine light stabilizer having a base constant of 5 to 10; a fluorescent dye containing a perylene bisimide-based compound; binder resin; photopolymerizable compounds; photoinitiator; And a self-luminous photosensitive resin composition comprising a solvent. According to claim 1,
The hindered amine-based light stabilizer is a self-luminous photosensitive resin composition, characterized in that it comprises a compound containing the structure of Formula 1 in the molecular structure.
[Formula 1]

(In Formula 1,
R ₁ to R ₄ are each independently hydrogen, (C ₁ to C ₇ )alkyl group, hydroxy-(C ₁ to C ₇ )alkyl group, hydroxy-(C ₁ to C ₄ )alkyl group (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkoxy group or (C ₁ to C ₄ )alkoxycarbonyl group, or
R ₁ and R ₂ ; Or R ₃ and R ₄ ; each of which shares a C atom adjacent to each other (C ₃ to C ₇ ) A cycloalkyl group;
Ra or Rb is each independently hydrogen, (C ₁ to C ₄ )alkyl group, hydroxy-(C ₁ to C ₄ )alkyl group, (C ₆ to C ₁₀ )aryl group, (C ₆ to C ₁₀ )aryl- (C ₁ to C ₄ )alkyl group, (C ₁ to C ₄ )alkyl-(C ₉ to C ₁₀ )aryl group, cyano group, (C ₁ to C ₄ )alkoxycarbonyl group, (C ₁ to C ₄ )alkoxycar Bornyl-(C ₁ to C ₄ )alkyl group, mono-(C ₁ to C ₄ )alkylcarbamoyl group, di-(C ₁ to C ₄ )alkylcarbamoyl group, mono-2-hydroxyethylcarbamoyl group, di-2-hydroxyethyl carbamoyl group, 1-hydroxy-2-hydroxymethyl-2-propyl carbamoyl group, 1,1-dihydroxymethyl-2-hydroxycarbamoyl group, amidino group, 2-imidazolyl group or -P=O(O-(C ₁ to C ₄ )alkyl) ₂ or
Ra and Rb are each bonded to each other as a divalent group to form a 5- to 8-membered aliphatic or aromatic heterocycle with or without at least one hetero atom selected from the group consisting of N, O and S,
X is C or O;
A is hydrogen, -C(R ₅ ) ₃ ,
Each of R ₅ is independently hydrogen, a substituted or unsubstituted, (C ₁ to C ₁₂ )alkyl group, (C ₅ to C ₁₂ )cycloalkyl group, (C ₆ to C ₁₂ )aryl group, cyano group, (C ₁ to C ₁₂ )alkenyl group, (C ₁ to C ₁₂ )carbonyl group, (C ₁ to C ₁₂ )ester group, COR ₆ or -OC(=O)-CH ₂ CH ₂ -C(=O)- and ,
Each of R ₆ is independently a (C ₁ to C ₈ )alkyl group, (C ₆ to C ₁₂ )aryl group, (C ₁ to C ₈ )alkoxy group, or —N(R ₇ ) ₂ ,
R ₇ are each independently hydrogen or a (C ₁ to C ₈ )alkyl group, and among A, aryl is a (C ₁ to C ₁₂ )alkyl group, a halogen group, a (C ₁ to C ₁₂ )alkoxy group, (C ₁ to C ₁₂ ) Alkylcarbonyl group, glycidyloxy group, -OH, -COOH or -COO (C ₁ to C ₁₂ ) It is unsubstituted or substituted with an alkyl group.) According to claim 1,
The perylene bisimide-based compound is a self-luminous photosensitive resin composition, characterized in that it is a compound having a structure represented by the following Chemical Formula 2-2.
[Formula 2-2]

(In Formula 2-2,
R ₈ and R ₉ are each independently a (C ₁ to C ₁₀ ) aryl group unsubstituted or substituted with an alkyl group (C ₆ to C ₁₈ ),
R ₁₄ are each independently hydrogen, (C ₁ to C ₁₀ )alkyl group, (C ₆ to C ₁₈ )aryl group, (C ₇ to C ₁₈ )arylalkyl group, (C ₁ to C ₁₈ )alkoxy group, number of atoms 3 to 30, a heterocyclic group or a halogen group,
x is each independently an integer from 1 to 5,
When any one or more of x is 2 or more, _{the functional groups of R 14} corresponding thereto are the same or different from each other.) 4. The method of claim 3,
The self-luminous photosensitive resin composition, characterized in that the compound containing the structure of Formula 2-2 is at least one selected from the group consisting of compounds represented by the following Formulas 2-3 to 2-11.

According to claim 1,
The content of the light stabilizer is based on the solid content of the self-luminous photosensitive resin composition containing the light-emitting photosensitive resin composition, characterized in that it is included in an amount of 10 to 300 parts by weight based on the total weight of the photopolymerization initiator. According to claim 1,
The content of the fluorescent dye is a self-luminous photosensitive resin composition, characterized in that it is included in an amount of 0.1 to 10% by weight based on the total weight of the composition including the same. A color conversion layer comprising a cured product of the self-luminous photosensitive resin composition according to any one of claims 1 to 6. A color filter comprising the color conversion layer of claim 7. An image display device comprising the color filter of claim 8.

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