TWI680352B - Self emission type photosensitive resin composition, and color filter comprising thereof and display device comprising of the same - Google Patents

Abstract

The present invention relates to a self-luminous photosensitive resin composition, a color filter, and an image display device. More specifically, the present invention relates to a long-chain carboxyl group introduced into an acrylate side chain in a substructure including a designed component and an end introduced into the terminal. A highly reactive (meth) acrylate-based alkali-soluble resin, a quantum dot, a photopolymerizable compound, a self-luminous photosensitive resin composition containing a photopolymerization initiator, a color filter including the same, and an image display device. The above-mentioned alkali-soluble resin more effectively protects the quantum dots, and effectively prevents a decrease in the luminous efficiency of the quantum dots after the hard-baking process, thereby providing a high-quality color filter with excellent luminance characteristics.

Description

Self-luminous photosensitive resin composition, color filter, and image display device

The present invention relates to a self-luminous photosensitive resin composition, a color filter, and an image display device including the self-luminous photosensitive resin composition which can effectively prevent a decrease in luminous efficiency of a quantum dot after a hard-baking process.

The color filter is a thin film type optical component that can extract three colors of red, green, and blue from white light to form a fine pixel unit. The size of a pixel is about tens to hundreds of microns. This type of color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate in order to shield the boundary between each pixel, and a plurality of colors (typically red (R), green) for forming each pixel. (G) and blue (B) 3 primary colors) are structured by sequentially stacking pixel portions arranged in a predetermined order. Generally speaking, a color filter can be manufactured by coating three or more colors on a transparent substrate using a dyeing method, an electrodeposition method, a printing method, or a pigment dispersion method. In recent years, pigments using a pigment-dispersed photosensitive resin have been used. Decentralized methods have become mainstream.

One of the methods of forming a color filter is a pigment dispersion method in which a colored film is formed by repeating a series of processes in which a transparent matrix with a black matrix is coated with a colorant, an alkali-soluble resin, and a photopolymerizable monomer. The photosensitive resin composition of a polymer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives, after exposing a pattern in a form to be formed, remove non-exposed parts with a solvent and perform thermal curing. Active applications in LCDs for laptops, monitors, TVs, etc. Recently, the actual situation is that, for a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages, not only excellent pattern characteristics are required, but also higher efficiency such as high color reproduction rate, high brightness, and high contrast is required.

However, color reproduction is achieved by a light-transmitting filter irradiated by a light source. In the process, a part of the light is absorbed by the color filter, thereby reducing the light efficiency. In addition, due to the characteristics of the pigment as a color filter, there is The fundamental limitation of not being able to achieve perfect color reproduction.

As a solution that can solve such problems, there is a method for manufacturing a color filter using a quantum dot photosensitive resin composition.

Korean Patent Publication No. 2007-0094679 discloses that color reproducibility can be improved by having a color filter layer formed of a quantum dot (Quantum Dot). Korean Patent Publication No. 2009-0036373 discloses that by using quantum The light emitting layer formed by dot phosphors can replace the conventional color filter, which can improve the light emitting efficiency and improve the display quality.

In this way, in the case where the quantum dot is used as a light-emitting substance of a color filter, the light-emitting waveform can be narrowed, and it has a high color expression ability that cannot be exhibited by a pigment, and has excellent luminance characteristics. However, when the hard-baking process performed in the manufacture of a color filter is performed, crystals or the like are generated on the surface due to the low stability of the quantum dots, which causes a problem that the luminous efficiency of the quantum dots is greatly reduced.

Prior art literature Patent literature

Patent Document 1: Korean Patent Publication No. 2007-0094679

Patent Document 2: Korean Patent Publication No. 2009-0036373

In response to this, the applicant has conducted various measures in order to suppress the decrease in the efficiency of the quantum dots. As a result of the research, it was confirmed that when an alkali-soluble resin designed to introduce a long-chain carboxyl group into an acrylate side chain and a highly reactive (meth) acrylate group at a terminal is used, quantum dots can be protected more effectively, thereby The present invention has been completed.

Therefore, an object of the present invention is to provide a color filter that can effectively prevent the luminous efficiency of the quantum dots from decreasing.

In addition, another object of the present invention is to provide an image display device having high luminance characteristics by including the color filter.

To achieve the above object, the present invention provides a self-luminous photosensitive resin composition including a quantum dot, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator.

Among them, the alkali-soluble resin is characterized by including a repeating unit represented by the following Chemical Formula 1.

(In the above Chemical Formula 1, R ₁ is hydrogen or methyl, and R ₂ is a C1-C30 alkyl group, a C1-C30 alkyloxy group, or a C3-C30 alkyloxycarbonylaminoalkyl group, wherein, The alkyl group, alkyloxy group or alkyloxycarbonylaminoalkyl group may be an alkyl group of C1 to C20, an alkoxy group of C1 to C20, an aralkyl group of C6 to C20, an aryl group of C6 to C20, C2 ~ C20 fluorenyl, C2 ~ C20 fluorenyl, C2 ~ C20 alkoxycarbonyl, C7 ~ C20 arylcarbonyl, C2 ~ C20 dialkylamino, C1 ~ C20 alkylamino , Halogen atom, cyano, furyl, furfuryl, tetrahydrofuranyl, tetrahydrofurfuryl, C1-C20 alkylthio, trimethylsilyl, trifluoromethyl, carboxyl, thienyl, morpholino Or morpholino carbonyl, R _{3 is} represented by -R ₅ -R ₆ -COOH, where R ₅ is -OC (= O)-, and R ₆ contains C1-C30 alkylene and C2-C30 vinyl Alkenyl, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N -(R ₁₄ R ₁₅ )-, -RC (= O) -NR ₁₆ -C (= O) R _17- , -R ₁₈ -C (= O) -N (R ₁₉ ) (C (= O)) -R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OCR _25- , -CH = CH- OC (= O) -N (R ₂₆ ) (R ₂₇ )-, C6 ~ C3 0, aryl, C5 to C30, heteroaryl, C6 to C30, cycloalkyl, wherein R ₇ to R ₂₇ are the same or different from each other, and are each independently hydrogen, C1 to C30, alkyl, C6 ~ C30 extended aryl or C6 ~ C30 extended cycloalkyl, where R ₆ can pass through C1 ~ C20 alkyl, C1 ~ C20 alkoxy, C6 ~ C20 aralkyl, C6 ~ C20 Aryl, C2 ~ C20 fluorenyl, C2 ~ C20 fluorenyl, C2 ~ C20 alkoxycarbonyl, C7 ~ C20 arylcarbonyl, C2 ~ C20 dialkylamine, C1 ~ C20 Alkylamino, halogen, cyano, furanyl, furfuryl, tetrahydrofuranyl, tetrahydrofurfuryl, C1-C20 alkylthio, trimethylsilyl, trifluoromethyl, carboxyl, thienyl , Morpholino or morpholinocarbonyl, and R ₄ is an alkyl (meth) acrylate group of C4 to C20.)

The present invention also provides a color filter including the above-mentioned self-luminous photosensitive resin composition.

The present invention also provides an image display device including the color filter.

When the quantum dot photosensitive resin composition containing the alkali-soluble resin of the present invention is used to form a pixel of a color filter, the decrease in luminous efficiency of the quantum dots and the poor photosensitive characteristics caused after the hard-baking process can be eliminated, thereby providing brightness. High-quality color filters with excellent characteristics.

The invention discloses a self-luminous photosensitive resin composition which can be used in a color filter of an image display device.

<Self-light-emitting photosensitive resin composition>

In the case of quantum dots used in color filters instead of pigments and dyes, color expression is achieved by releasing self-luminescence. At this time, the instability of the quantum dots reduces the efficiency of spontaneously released light, which is especially useful for This occurs severely during the hard bake process of manufacturing color filters. In this regard, the present invention discloses a self-luminous photosensitive resin composition having an alkali-soluble resin having a specific functional group that can effectively suppress the above-mentioned decrease in light efficiency by protecting the surface of a quantum dot, And the chain length is controlled.

Alkali soluble resin

The alkali-soluble resin functions to make the non-exposed portion of the photosensitive resin layer alkali-soluble and to remove it, and to leave the exposed area. In addition to the above functions, the alkali-soluble resin according to the present invention also functions as a protective group, so that the quantum dot particles are uniformly dispersed in the composition, and no defects are generated on the surface of the quantum dots in the coating process.

Such an alkali-soluble resin has a long-chain carboxyl group and a (meth) acrylate group in a molecular structure, and is preferably represented by the following Chemical Formula 1.

(In the above Chemical Formula 1, R ₁ is hydrogen or methyl, and R ₂ is a C1-C30 alkyl group, a C1-C30 alkyloxy group, or a C3-C30 alkyloxycarbonylaminoalkyl group, wherein, The above alkyl, alkyloxy or alkyloxycarbonylaminoalkyl may be C1 to C20 alkyl, C1 to C20 alkoxy, C6 to C20 aralkyl, C6 to C20 aryl, C2 ~ C20 fluorenyl, C2 ~ C20 fluorenyl, C2 ~ C20 alkoxycarbonyl, C7 ~ C20 arylcarbonyl, C2 ~ C20 dialkylamino, C1 ~ C20 alkylamino , Halogen atom, cyano, furyl, furfuryl, tetrahydrofuranyl, tetrahydrofurfuryl, C1-C20 alkylthio, trimethylsilyl, trifluoromethyl, carboxyl, thienyl, morpholino Or morpholino carbonyl, R _{3 is} represented by -R ₅ -R ₆ -COOH, where R ₅ is -OC (= O)-, and R ₆ contains C1-C30 alkylene and C2-C30 vinyl Alkenyl, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N -(R ₁₄ R ₁₅ )-, -RC (= O) -NR ₁₆ -C (= O) R _17- , -R ₁₈ -C (= O) -N (R ₁₉ ) (C (= O)) -R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OCR _25- , -CH = CH- OC (= O) -N (R ₂₆ ) (R ₂₇ )-, C6 ~ C30 extended aryl, C5 ~ C30 extended heteroaryl, C6 ~ C30 extended cycloalkyl, wherein R ₇ to R ₂₇ are the same or different from each other, and each is independently hydrogen, C1 ~ C30 extended alkyl , C6 ~ C30 extended aryl or C6 ~ C30 extended cycloalkyl, among which, R ₆ can be passed through C1 ~ C20 alkyl, C1 ~ C20 alkoxy, C6 ~ C20 aralkyl, C6 ~ C20 aryl, C2 to C20 fluorenyl, C2 to C20 fluorenyl, C2 to C20 alkoxycarbonyl, C7 to C20 arylcarbonyl, C2 to C20 dialkylamino, C1 to C20 Alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, C1-C20 alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thiophene Group, morpholino group or morpholinocarbonyl group, and R ₄ is an alkyl (meth) acrylate group of C4 to C20.)

。 Preferably, R ₂ is a C1-C20 alkyl group, a C1-C20 alkyloxy group, or a C3-C20 alkyloxycarbonylaminoalkyl group. More preferably, R _{2 is} particularly preferably a methine group, an ethinyl group, a propylidene group, a butylidene group, an oxyethyloxy group, a secondary ethyloxy group, a tertiary ethyloxy group, an oxyethyloxycarbonyl group. Aminoethyl, in this case, they are trivalent functional groups, most preferably

.

Preferably, R ₆ is an alkylene group of C1 to C20, an alkylene group of C2 to C20, an alkylene group of C6 to C20, or a cycloalkylene group of C6 to C20, which may be substituted or unsubstituted by a carboxyl group. .

More preferably, R _{6 is} particularly preferably methylene, ethylidene, propylidene, isopropylidene, pentylyl, vinylidene, 2-methyl-vinylidene, dimethylethylene, Butyl, cyclohexyl, 4-cyclohexenyl, bicyclo [4.4.0] decane, bicyclo [2.2.1] -2-heptenyl, phenylene, carboxyphenylene or naphthalene base.

R _{4 is} preferably an alkyl (meth) acrylate group of C 4 to C 12, more preferably an acrylate group or a methacrylate group.

In this specification, the "alkyl" mentioned includes straight-chain or branched-chain types. As examples, it includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group and the like, the term "alkylene" means a divalent form of an alkyl group.

In this specification, "aryl" mentioned includes phenyl, biphenyl, terphenyl, stilyl, naphthyl, anthracenyl, phenanthryl or fluorenyl, etc. The term "aryl" means 2 of aryl Valent pattern.

In this specification, "cycloalkyl" includes cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, norbornyl and norbornenyl, and bicyclic rings as their condensed forms. Amyl, dicyclohexyl, dicycloheptyl, diadamantyl, dibornyl, dinorbornyl, or dinorbornyl, etc. The term "cycloalkyl" means the divalent form of cycloalkyl.

Preferably, the repeating unit of the above Chemical Formula 1 may have a structure of a compound of the following Chemical Formulas 2 to 31, wherein the functional groups are arranged in Table 1 below.

[Chemical Formula 7]

[Chemical Formula 11]

[Chemical Formula 15]

[Chemical Formula 19]

[Chemical Formula 28]

In the present invention, the alkali-soluble resin preferably has a polystyrene-equivalent weight average molecular weight in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight-average molecular weight of the alkali-soluble resin is in the range of 3,000 to 100,000, it is preferred that the film of the exposed portion is less likely to be developed during development and the solubility of the non-exposed portion is good.

The acid value of the alkali-soluble resin of the present invention is preferably in the range of 30 to 150 mgKOH / g based on the solid content. When the acid value is less than 30 mgKOH / g, there is a concern that the solubility of the alkaline developing solution is lowered and a residue is left on the substrate. When the acid value exceeds 150 mgKOH / g, the possibility of pattern peeling becomes high. .

The molecular weight distribution of the alkali-soluble resin is preferably 1.0 to 6.0, and more preferably 1.5 to 4.0. When the molecular weight distribution is 1.0 to 6.0, it is excellent in developability, so it is preferable.

The alkali-soluble resin according to the present invention may be a homopolymer containing the repeating unit of the above Chemical Formula 1 alone, or may be a copolymer with other unsaturated monomers. Among them, in the case of a copolymer, it may be in the form of an alternating copolymer, a random copolymer, or a block copolymer, and is not particularly limited in the present invention.

The copolymerizable unsaturated monomer may be (i) a carboxyl group-containing unsaturated monomer, and / or (ii) a glycidyl group-containing unsaturated monomer, and (iii) other monomers having an unsaturated bond.

(i) The carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or the like. Specifically, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acid may also be a mono (2-methacryloxyalkyl) ester thereof, and examples thereof include mono (2-propenyloxyethyl) succinate and mono (2 -Methacryloxyethyl) ester, phthalic acid mono (2-acryloxyethyl) ester, Mono (2-methacryloxyethyl) phthalate and the like. In addition, the unsaturated polycarboxylic acid may be a mono (meth) acrylate of a double-ended carboxyl polymer, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylic acid. Esters, etc. These carboxyl group-containing monomers can be used alone or in combination of two or more kinds.

(ii) The glycidyl-containing unsaturated monomer may be o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, allyl glycidyl ether, Glycidyl acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxy cyclohexyl methyl (meth) acrylate, methyl glycidyl (meth) acrylate, etc. More preferably, it may be glycidyl (meth) acrylate, which may be used alone or in combination of two or more kinds.

(iii) Other monomers having unsaturated bonds can use styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, Aromatic vinyl compounds such as m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, indene; (methyl) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (formyl) Base) second butyl acrylate, third butyl (meth) acrylate, tricyclodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ester, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (methyl ) Acrylic-2-phenoxy Ester, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) Acrylate, isobornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, adamantane (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as propyl (meth) acrylate, glycerol mono (meth) acrylate; 2-aminoethyl acrylate, 2-aminoethyl (meth) acrylate, (methyl ) 2-dimethylaminoethyl acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-methyl (meth) acrylate Unsaturated carboxylic acid amino alkyl ester compounds such as aminopropyl ester, 3-dimethylaminopropyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate And other carboxylic acid vinyl ester compounds; unsaturated methyl ether, vinyl ether, allyl glycidyl ether and other unsaturated ether compounds; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene chloride, etc. Vinylation Thereof; acrylamide, methyl acrylamide, acrylamide alpha] chloride, N -2- hydroxyethyl acrylamide, N -2- hydroxyethyl methyl acrylamide unsaturated Amides; cis Unsaturated fluorene imines such as butene difluorene imine, N -benzyl cis butene difluorene imide, N -phenyl cis butene difluorene imine, N -cyclohexyl cis butene difluorene imine; Monomers such as 1,3-butadiene, isoprene, chloroprene and other aliphatic conjugated diene.

In order to easily disperse the quantum dots and maintain a high luminous efficiency in the process, such alkali-soluble resins contain 5 to 80% by weight of the total self-luminous photosensitive resin, preferably 10 to 10, based on the solid content. Use within 70% by weight. If the content is lower than the above range, it is difficult to form a coating film. On the other hand, if it exceeds the above range, the content of other components is relatively reduced, and the function as a color filter is affected. Therefore, it is appropriately used within the above range.

Along with the above-mentioned alkali-soluble resin, the self-luminous photosensitive composition according to the present invention includes a quantum dot, a photopolymerizable compound, and a photopolymerization initiator. Hereinafter, each component will be described in more detail.

Quantum dot

Quantum dots are nanometer-sized semiconductor materials. Atoms form molecules. Molecules form nano particles by forming small molecular aggregates called molecular clusters. When such nano particles have semiconductor characteristics in particular, they are called quantum dots. When a quantum dot obtains energy from the outside and becomes an excited state, it will automatically release energy in accordance with the corresponding band gap.

The quantum dots used in the photosensitive resin composition of the present invention are photoluminescent quantum dot particles that can emit light by light irradiation.

The quantum dot according to the present invention is not particularly limited as long as it is a quantum dot that can emit light by the stimulation of light, and can be selected freely, for example, a group II-VI semiconductor compound, a group III-V semiconductor compound, or a group IV-VI semiconductor compound. , A group consisting of a group IV element or a compound containing the same, and the like. These can be used individually or in mixture of 2 or more types.

The above II-VI semiconductor compounds may be selected from the group consisting of two-element compounds selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof. Selected from the group consisting of three elements of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and the mixture thereof A compound, and a four-element compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof; the above III-V semiconductor compounds may be selected from Group: a two-element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof, selected from the group consisting of GaNP, GaAs, GaNSb, GaPAs Three-element compounds in the group consisting of GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof, and selected from the group consisting of A four-element compound in the group consisting of a mixture of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and the like; the above-mentioned Group IV-VI semiconductor compounds may be Selected from the group consisting of two elemental compounds selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof, selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, Three-element compounds in the group consisting of SnPbS, SnPbSe, SnPbTe, and mixtures thereof, and four-element compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof; the above-mentioned Group IV elements or compounds containing the same A group consisting of an elemental compound selected from the group consisting of a mixture of Si, Ge, and the like, and a two-element compound selected from the group consisting of a mixture of SiC, SiGe, and the like can be selected.

In addition, the above quantum dots may have a homogeneous single structure, a dual structure such as a core-shell, a gradient structure, or a mixed structure thereof.

In the above-mentioned core-shell dual structure, a substance forming each core and shell may be formed of the semiconductor compounds different from each other mentioned above. For example, the core may include one or more substances selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more substances selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

The coloring photosensitive resin composition generally used in the manufacture of color filters may contain red, green, and blue colorants in order to display colors. Similarly, the quantum dots of the present invention can also be divided into quantum dots expressing red and green dots. The quantum dots and the quantum dots expressing blue may be one selected from the foregoing combinations of red, green, blue, and the like.

The above quantum dots can be synthesized using a wet chemical process, an organometallic chemical deposition process, or a molecular beam epitaxy process.

The wet chemical method is a method in which a precursor substance is added to an organic solvent to grow particles. When crystals grow, organic solvents are naturally located on the surface of the quantum dot crystals to act as dispersants, thereby regulating the growth of the crystals. Therefore, they are related to the metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MOCVD) described above. Compared with vapor deposition methods such as MBE, molecular beam epitaxy), the growth of nano particles can be controlled by an easier and cheaper process.

The content of the quantum dot particles according to the present invention is not particularly limited, and may be included in the total weight of the solid content of the self-luminous photosensitive resin composition, for example, from 3 to 80% by weight, preferably from 5 to 70% by weight. If the content is less than 3% by weight, the luminous efficiency is very small, and if it exceeds 80% by weight, there is a problem that it is difficult to form a pixel pattern because the content of other components is relatively insufficient.

Photopolymerizable compound

Along with such quantum dots, the self-luminous photosensitive resin composition according to the present invention contains a photopolymerizable compound.

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and others. Polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy Ethyl acrylate, N-vinyl pyrrolidone and the like. 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 (propylene ethoxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the other polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trihydroxy Methylpropane tri (meth) acrylate, isopentaerythritol tri (meth) acrylate, isopentaerythritol tetra (meth) acrylate, diisopentaerythritol penta (meth) acrylate, ethoxylate Diisopentaerythritol hexa (meth) acrylate, propoxylated diisopentaerythritol hexa (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, like the following chemical formula 32 Diisopentaerythritol (poly) acrylate having a hydroxyl group or a carboxylic acid group as in Chemical Formula 33.

[Chemical Formula 32]

(In the above Chemical Formula 32, R ₂₈ is an acrylate group or a methacrylate group, and R ₂₉ is hydrogen, acrylfluorenyl, or methacrylfluorenyl.)

，其中，R₃₅及R₃₆為丙烯酸酯基或甲基丙烯酸酯基，R₃₇為氫、丙烯醯基、甲基丙烯醯基或-C(=O)CH₂CH₂C(=O)OH，R₃₃為-C(=O)CH₂CH₂C(=O)OH。 (In the above Chemical Formula 33, R ₃₀ to R ₃₃ are the same as or different from each other, and are OH, C1-C4 alkyl, acrylate, methacrylate or -OR ₃₄ , respectively. At least one of the above R ₃₀ to R ₃₃ is an acrylate group or a methacrylate group, R ₃₄ is

, Where R ₃₅ and R ₃₆ are acrylate or methacrylate groups, and R ₃₇ is hydrogen, propylene acryl, methacryl, or -C (= O) CH ₂ CH ₂ C (= O) OH R ₃₃ is -C (= O) CH ₂ CH ₂ C (= O) OH.

As for the photopolymerizable compound of the present invention, a bifunctional or higher polyfunctional monomer can be used for these compounds, and a 5-functional photopolymerizable compound containing a carboxylic acid group is more preferably used.

When a 5-functional or more photopolymerizable compound is used, the formation of a pixel pattern is more excellent. Especially in the case of a 5-functional photopolymerizable compound containing a carboxylic acid group, There is a reduction in light emission characteristics due to the aggregation of quantum dot particles, which is excellent in photoreactivity, so that a pixel pattern having excellent light emission properties can be formed.

The content of the photopolymerizable compound is used in a range of 5 to 50% by weight, and preferably in a range of 7 to 45% by weight based on 100% by weight of the self-luminous photosensitive resin composition. However, when the photopolymerizable compound is used within the aforementioned content range, a pixel pattern is easily formed in a light source, and the strength or smoothness of the pixel portion becomes good. If the content is lower than the above range, the degree of photo-curing caused by light is reduced and it is difficult to form a pixel pattern. On the other hand, if the content exceeds the above range, the pattern may peel off.

Photopolymerization initiator

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention is not limited, and it is one or more compounds selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound. . The self-luminous photosensitive resin composition containing the above-mentioned photopolymerization initiator is highly sensitive, and a pixel formed using the composition can improve the strength or patternability of the pixel portion.

The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention is not limited, and it is one or more compounds selected from the group consisting of a triazine compound, an acetophenone compound, a biimidazole compound, and an oxime compound. . The self-luminous photosensitive resin composition containing the above-mentioned photopolymerization initiator is highly sensitive, and a pixel formed using the composition can improve the strength or patternability of the pixel portion.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (tri (Chloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl ) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tri Azine Wait.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, and 2-hydroxy -1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthio (Phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy- An oligomer of 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one and the like. Moreover, the compound represented by the following chemical formula 34 is mentioned.

(In the above Chemical Formula 34, R ₃₈ to R ₄₁ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C2 alkyl-substituted or unsubstituted phenyl group, a C1-C12-alkyl group, or unsubstituted (Substituted benzyl, or C1-C12 alkyl substituted or unsubstituted naphthyl.)

Specific examples of the compound represented by the above Chemical Formula 34 include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one and 2-ethyl-2-amino ( 4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino ( 4-morpholinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4 -Morpholinophenyl) butane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propane-1-one, 2-ethyl-2-amino (4- Morpholinophenyl) butane-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 2-methyl-2-dimethylamine (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one, and the like.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkane) Oxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4,4', 5 At the 5 'position Instead of imidazole compounds. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) are preferably used ) -4,4 ', 5,5'-tetraphenylbiimidazole.

Examples of the oxime compound include the following Chemical Formula 35, Chemical Formula 36, and Chemical Formula 37.

In addition, to the extent that the effects of the present invention are not impaired, other photopolymerization initiators and the like commonly used in this technology can be used. Examples of the photopolymerization initiator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These can be used individually or in combination of 2 or more types.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based compound include benzophenone, methyl benzophenone benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis ( N, N ' -di Methylamino) -benzophenone and the like.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy Thioxanthone and so on.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9 , 10-diethoxyanthracene and the like.

Other examples include 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzoin, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. as other photopolymerization initiators.

In addition, when a photopolymerization initiator is used in combination with a photopolymerization initiator, a self-luminous photosensitive resin composition containing the same achieves higher sensitivity and improves productivity when forming a color filter using the composition. good.

In addition, as the photopolymerization initiation aid that can be used in combination with a photopolymerization initiator in the present invention, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and the like can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-diamine. Methylaminobenzoate, 4-dimethylaminobenzoate isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, N, N -dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as mignonone), 4,4'-bis (diethylamino) benzoyl Aromatic amine compounds such as ketones. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthiothioate. Acetic acid, methoxyphenyl thioacetic acid, dimethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N -phenylglycine, phenoxyacetic acid, naphthalene yl thioacetic acid, N - glycine naphthyl group, a naphthyl group, an aromatic hetero atoms such as acetic acid class.

In the self-luminous photosensitive resin composition of the present invention, the content of the photopolymerization initiator is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the solid content within 100% by weight of the entire composition. The amount of the initiator used is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the above-mentioned reference.

When the use amount of the photopolymerization initiator is in the above range, it is preferable because the self-luminous photosensitive resin composition has a high sensitivity and the strength of the pixel portion or the smoothness of the surface of the pixel portion tends to be good. In addition, if the amount of the photopolymerization initiation aid is in the above range, the sensitivity efficiency of the self-luminous photosensitive resin composition tends to be higher, and the productivity of a color filter formed using the composition tends to be improved. Better.

additive

In addition to the above components, the self-luminous photosensitive resin composition of the present invention may further include a UV stabilizer, a filler, other polymer compounds, a curing agent, a dispersant, an adhesion promoter, an antioxidant, an anticoagulant, and the like, as necessary.

The said UV stabilizer is added to a photosensitive resin composition, and the light resistance can be ensured.

Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, and o- Aminobenzoate derivatives, benzophenamethane derivatives, and the like.

Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4. -Methoxybenzophenone and 2,4-dihydroxybenzophenone.

Specific examples of the benzoate derivative include 2-ethylhexylsalicylate, phenylsalicylate, p-third-butylphenylsalicylate, and 2,4-secondary Butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, cetyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like.

Specific examples of the benzotriazole derivative include 2- (2'-hydroxy-5'-third butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-formaldehyde). Phenyl) benzotriazole, 2- (2'-hydroxy-3'- Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzo Triazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-third-pentylphenyl) benzotriazole Wait.

Specific examples of the triazine derivative include hydroxyphenyltriazine, diethylhexyloxyphenolmethoxymethoxytriazine, and the like.

The aforementioned UV stabilizers may also be commercially available products, and examples thereof include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 1577, CHIMASSORB81 (above, Ciba refined manufacturing, trade name) and so on.

In the wavelength region, it is preferable that the UV stabilizer has a maximum absorption region below 350 nm (including the j-ray). A UV stabilizer having a maximum absorption region of 350 nm or more has a concern that the irradiation intensity of the i-ray is weakened. As far as the structure of UV stabilizers is concerned, benzophenone derivatives and triazine derivatives have good absorption regions below 350 nm. As corresponding commercially available products, TINUVIN 400, TINUVIN 1577, CHIMASSORB81 and the like can be cited as better examples.

The said UV stabilizer can be used individually by 1 type or in combination of 2 or more types, and can ensure the light resistance and yellowing prevention of the photosensitive resin composition of this invention.

Specific examples of the filler include glass, silicon dioxide, and alumina.

Specific examples of the other high-molecular compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohols, polyacrylic acids, polyethylene glycol monoalkyl ethers, and polyfluoroalkanes. Thermoplastic resins such as acrylic, polyester and polyurethane.

The curing agent is used to improve deep-layer curing and mechanical strength. Examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, and oxetane compounds.

Examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, and novolac type. Epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins, and brominated resins Aliphatic, cycloaliphatic or aromatic epoxy compounds other than derivatives, butadiene (co) polymer epoxides, isoprene (co) polymer epoxides, glycidyl (meth) acrylates (Co) polymers, triglycidyl isocyanurate, and the like.

Examples of the oxetane compound in the curing agent include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and terephthalic acid. Ester dioxetane, cyclohexanedicarboxylic acid dioxetane and the like.

Together with the curing agent, the curing agent may further include a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound. Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. As the carboxylic acid anhydride, a commercially available substance can be used as the epoxy resin curing agent. Examples of the epoxy resin curing agent include a trade name (ADEKA HARDENER EH-700) (manufactured by ADEKA Industry Co., Ltd.), a trade name (RIKACID HH) (manufactured by Shin Nihon Chemical Co., Ltd.), and a trade name (MH -700) (manufactured by Shin Nihon Chemical Co., Ltd.) and the like. The said hardening | curing agent can be used individually or in mixture of 2 or more types.

As the dispersant, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, and amphoteric surfactants. These can be used individually or in combination of 2 or more types. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and tertiary In addition to amine-modified polyurethanes and polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), and EFTOP ( (Manufactured by Tohkem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zenica), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.) )Wait.

These dispersants can be used individually or in combination of two or more kinds, and may generally contain 0.01 to 15% by weight based on the solid content in the photosensitive resin composition.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl). 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate Propyl trimethoxysilane, 3-isocyanate propyltriethoxysilane and the like. These adhesion promoters can be used alone or in combination of two or more kinds. The solid content in the photosensitive resin composition may generally include 0.01 to 10% by weight, and preferably 0.05 to 2% by weight. %.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-third-butylphenol) and 2,6-di-third-butyl-4-methylphenol. Wait.

Specific examples of the anticoagulant include sodium polyacrylate.

Solvent

The self-luminous photosensitive resin composition containing the above-mentioned alkali-soluble resin can be produced by dissolving or dispersing in a solvent for coating. The solvent according to the present invention is not particularly limited, and may be an organic solvent generally used in the technology.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, and diethylene glycol dimethyl ether. Diethylene glycol Diethylene glycol dialkyl ethers such as alcohol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ethers such as methyl acetate cellosolve and ethyl cellosolve Acetates, propylene glycol alkyl ethers such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetic acid Alkyl glycol alkyl ether acetates such as esters, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl Ketones such as ketones and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Esters such as methyl esters, cyclic esters such as γ-butyrolactone, and the like. These can be used individually or in mixture of 2 or more types.

Regarding the above-mentioned solvents, since the viscosity changes depending on the coating method or device, the content should be appropriately adjusted so that the concentration of the self-luminous photosensitive resin composition having the above composition is 5 to 90% by weight, and preferably 20 to 80%. weight%.

The production of the self-luminous photosensitive resin composition containing the aforementioned composition is not particularly limited in the present invention, and a known method of mixing the respective compositions at an appropriate ratio can be used.

<Color filter>

In addition, the present invention can be preferably used as a color filter manufactured from the above-mentioned self-luminous photosensitive resin composition.

The manufacturing of the color filter includes: a step of coating the self-luminous photosensitive resin composition according to the present invention on a substrate; a step of selectively exposing a partial area of the above-mentioned photosensitive resin composition; and the above-mentioned photosensitive resin A step of removing exposed or unexposed areas of the composition.

The color filter obtained through such steps includes pixels formed by forming the photosensitive resin composition into a predetermined pattern and then exposing and developing the photosensitive resin composition.

In the case where the color filter of the present invention is applied to an image display device, light is emitted from the light source of the display device, and therefore, it can exhibit more excellent light efficiency. In addition, since color-releasing light is released, color reproducibility is more excellent, and since photoluminescence is used, Light is released in all directions, so the viewing angle can also be improved.

The color filter includes a substrate and a pattern layer formed on the substrate.

Regarding the substrate, the color filter itself may be a substrate, and may also be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be a glass substrate, a silicon (Si) substrate, a silicon oxide (SiO _x ) substrate, or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC). .

The pattern layer is a layer containing the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and then exposing, developing, and thermally curing in a predetermined pattern.

The pattern layer formed of the 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.

When applied to an image display device in such a case, the light emitted from the light source is not particularly limited, and a light source that emits blue light can be used in terms of more excellent color reproducibility.

According to another embodiment of the present invention, the pattern layer may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the pattern layer may further include a transparent pattern layer that does not contain quantum dot particles.

In the case where the pattern layer has only two colors, a light source that emits light of a wavelength showing a remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to express blue.

The color filter including the substrate and the pattern layer may further include a spacer formed between the patterns, and may further include a black matrix. It is also possible to include a drawing formed on a color filter Protective film on the top of the case.

<Image display device>

In addition, the present invention provides an image display device including the color filter.

The color filter of the present invention can be used not only in conventional liquid crystal display devices, but also in various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.

The image display device of the present invention may include a color filter including 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. In this case, when applied to an image display device, the light emitted from the light source is not particularly limited. From the viewpoint of more excellent color reproducibility, a light source that emits blue light is preferably used.

According to another embodiment of the present invention, the image display device of the present invention may further include a color filter including a pattern layer of only two colors among a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the color filter further includes a transparent pattern layer containing no quantum dot particles.

In the case where the pattern layer has only two colors, a light source that emits light of a wavelength showing a remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to express blue.

The image display device of the present invention is excellent in light efficiency, exhibits high luminance, has excellent color reproducibility, and has a wide viewing angle.

In the following, in order to help the understanding of the present invention and provide preferred embodiments, these embodiments are only used to illustrate the present invention, and do not limit the scope of the accompanying patent application. Those skilled in the art should be clear that in the present invention Within the scope and scope of technical ideas, various changes and modifications to the embodiments can be made. Such changes and modifications should also belong to the attached application. The range of benefits.

Manufacturing Example 1: Synthesis of Photoluminescence Green Quantum Dot Particle A with CdSe / ZnS Core-Shell Structure

Put CdO (0.4mmol), zinc acetate (4mmol) and oleic acid (5.5mL) together with 1-octadecene (20mL) into the reactor and heat to 150 ℃ to make it react. Thereafter, in order to remove the acetic acid generated by replacing oleic acid on zinc, the above reactants were placed under a vacuum of 100 mTorr for 20 minutes.

Next, heat was applied at 310 ° C to obtain a transparent mixture, and the mixture was maintained at 310 ° C for 20 minutes. Then, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine Se. The S and S solutions were quickly injected into a reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions.

After the thus-obtained mixture was allowed to grow at 310 ° C for 5 minutes, the growth was interrupted using an ice bath.

Next, it is precipitated with ethanol, the quantum dots are separated by a centrifugal separator, and excess impurities are washed with chloroform and ethanol to obtain oleic acid-stabilized particles with a total core particle diameter and shell thickness of 3 to 5 nm. CdSe (core) / ZnS (shell) quantum dot particle A.

Production Example 2: Synthesis of Alkali Soluble Resin (D1)

To a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 23 parts of 2-ethylhexyl acrylate were added. 1.6 parts of 4-methylstyrene, 46 parts of acrylic acid, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of glycidyl methacrylate were added and reacted at 100 ° C. 6 hours.

After that, the temperature of the reaction solution was lowered to normal temperature to obtain a resin (D1), and the synthesis was performed as such. The solid content acid value of the alkali-soluble resin was 100 mgKOH / g, and the weight average molecular weight (MW) measured by GPC was 6,500.

Production Example 3: Synthesis of Alkali Soluble Resin (D2)

To a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 21.4 parts of 2-ethylhexyl acrylate were added. 1.5 parts of 4-methylstyrene, 46 parts of glycidyl methacrylate, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of propionic acid were added and reacted at 100 ° C for 6 hours.

Thereafter, the temperature of the reaction solution was lowered to normal temperature, 6.0 parts of succinic anhydride was added, and the reaction was performed at 80 ° C for 6 hours. Thereby, a resin (D2) was obtained. The solid content acid value of the alkali-soluble resin synthesized in this way was 35 mgKOH / g, and the weight-average molecular weight (MW) measured by GPC was 6,300.

Production Example 4: Synthesis of alkali-soluble resin (D3)

To a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 21.4 parts of 2-ethylhexyl acrylate were added. 1.5 parts of 4-methylstyrene, 46 parts of glycidyl methacrylate, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of acrylic acid were added, and reacted at 100 ° C. for 6 hours.

After that, the temperature of the reaction solution was lowered to normal temperature, 6.0 parts of succinic anhydride was added, and the reaction was performed at 80 ° C for 6 hours. Thus, a resin (D3) was obtained. The solid content acid value of the alkali-soluble resin synthesized as described above was 33 mgKOH / g, and the weight average molecular weight (MW) measured by GPC was 6,350.

Production Example 5: Synthesis of alkali-soluble resin (D4)

To a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 21.4 parts of 2-ethylhexyl acrylate were added. 1.5 parts of 4-methylstyrene, 46 parts of glycidyl methacrylate, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of acrylic acid were added, and reacted at 100 ° C. for 6 hours.

After that, the temperature of the reaction solution was lowered to normal temperature, 12.5 parts of succinic anhydride was added, and the reaction was performed at 80 ° C. for 6 hours. Thereby, a resin (D4) was obtained. The solid content acid value of the alkali-soluble resin synthesized in this way was 69 mgKOH / g, and the weight average molecular weight (MW) measured by GPC was 5580.

Production Example 6: Synthesis of alkali-soluble resin (D5)

To a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube, 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, and 21.4 parts of 2-ethylhexyl acrylate were added. 1.5 parts of 4-methylstyrene, 46 parts of glycidyl methacrylate, 3 parts of n-dodecyl mercaptan, and nitrogen substitution. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of acrylic acid were added, and reacted at 100 ° C. for 6 hours.

After that, the temperature of the reaction solution was lowered to normal temperature, 12.5 parts of glutaric anhydride was added, and the reaction was performed at 80 ° C. for 6 hours. Thereby, a resin (D5) was obtained. The solid content acid value of the alkali-soluble resin synthesized as described above was 70 mgKOH / g, and the weight average molecular weight (MW) measured by GPC was 5600.

Production Example 7: Synthesis of alkali-soluble resin (D6)

To a tank equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen introduction tube Add 100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 21.4 parts of 2-ethylhexyl acrylate, 1.5 parts of 4-methylstyrene, and 46 parts of glycidyl methacrylate 3 parts of n-dodecyl mercaptan and nitrogen replacement. After that, the temperature of the reaction solution was raised to 80 ° C. with stirring, and the reaction was performed for 4 hours.

Next, the temperature of the reaction solution was lowered to normal temperature, and the atmosphere of the flask was replaced with nitrogen from air, and then 0.2 parts of triethylamine, 0.1 parts of 4-methoxyphenol, and 23.3 parts of acrylic acid were added, and reacted at 100 ° C. for 6 hours.

After that, the temperature of the reaction solution was lowered to normal temperature, 12.5 parts of phthalic anhydride was added, and the reaction was performed at 80 ° C. for 6 hours. Thus, a resin (D6) was obtained. The solid content acid value of the alkali-soluble resin synthesized as described above was 75 mgKOH / g, and the weight average molecular weight (MW) measured by GPC was 6,500.

Molecular weight evaluation

The weight-average molecular weight (Mw) of each of the alkali-soluble resins produced as described above was measured by the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series)

Column temperature: 40 ° C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0ml / min

Injection volume: 50μl

Detector: RI

Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Calibration Standards: TSK Standard Polystyrene (TSK STANDARD POLYSTYRENE) F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Solid content

Weigh about 1g of polymer solution and put it in an aluminum cup, add about 3g of acetone to dissolve After that, it dries naturally at normal temperature. Then, after drying under vacuum at 160 ° C. for 3 hours using a hot-air dryer (manufactured by Espec Corporation, trade name: PHH-101), it was allowed to cool in a dryer to measure the weight. The solid content of the polymer solution was calculated from the weight reduction.

Acid value

Weigh 3g of the resin solution and dissolve in a mixed solvent of 90g of acetone / 10g of water, use thymol blue as an indicator, and use a 0.1N KOH aqueous solution as a titration solution, using an automatic titration device (manufactured by Hiranuma Sangyo, trade name: COM-555) The acid value of the polymer solution is measured, and the acid value per 1 g of the solid content is obtained from the acid value of the solution and the solid content of the solution.

<Examples 1 to 4, Comparative Examples 1 to 2: Production of self-luminous photosensitive resin composition>

As shown in Table 2 below, after the components were mixed, they were diluted with propylene glycol monomethyl ether acetate so that the total solid content was 20% by weight, and then sufficiently stirred to obtain a self-luminous photosensitive resin composition.

5) Alkali-soluble resin produced in Production Example 2 6) Alkali-soluble resin produced in Production Example 3 7) Alkali-soluble resin produced in Production Example 4 8) Alkali-soluble resin produced in Production Example 9) In Production Example 6 Alkali-soluble resin produced 10) Alkali-soluble resin produced in Production Example 7

Experimental example 1: Manufacturing and evaluation of color filters

(1) Color filter manufacturing

A color filter was manufactured using the self-luminous photosensitive resin composition manufactured in Examples 1 to 4 and Comparative Examples 1 and 2.

That is, each of the above self-luminous photosensitive resin compositions was applied to a glass substrate by a spin coating method, then placed on a hot plate, and held at a temperature of 100 ° C. for 3 minutes to form a thin film. Next, a test mask having a transmission pattern with a length of 20 mm × 20 mm square and a line / gap pattern of 1 μm to 100 μm was placed on the film, and ultraviolet rays were irradiated at a distance of 100 μm from the test mask.

Among them, the ultra-high-pressure mercury lamp (trade name USH-250D) manufactured by USHIO Electric Co., Ltd. was used as the ultraviolet light source, and light was irradiated in the atmosphere at an exposure amount (365 nm) of 200 mJ / cm ² without using a special optical filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution at pH 10.5 for 80 seconds to develop. The glass plate with the film was washed with distilled water, then dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to produce a color filter pattern.

The film thickness of the self-luminous color filter pattern manufactured as described above was 3.0 μm.

(2) Luminous intensity measurement

For the pattern portion formed by the 20 mm × 20 mm square pattern in the color filter in which the above-mentioned self-luminous pixels are formed, the area where the light changes is measured by a 365 nm tube 4W UV irradiator (VL-4LC, VILBER LOURMAT), and a spectrometer (Ocean (Made by Optics) The luminous intensity of the 550 nm region of Examples 1 to 4 and Comparative Examples 1 to 2 was determined.

It can be judged that the higher the measured luminous intensity is, the more excellent the self-luminescence characteristics are exhibited. The measurement results of the luminous intensity are shown in Table 3 below.

The color filter was subjected to hard baking at 230 ° C. for 60 minutes. The luminous intensity before and after the hard baking was measured, and the level of the luminous efficiency was maintained. Table 3 shows the luminous intensity retention rate.

Referring to Table 3 above, it can be seen that in the case where the color filters of the self-luminous photosensitive resin compositions according to Examples 1 to 4 of the present invention are used, the luminous intensity retention rate after hard baking is also very high.

[Industrial availability]

By introducing the self-luminous photosensitive resin composition according to the present invention into a color filter of an image display device, excellent color reproduction characteristics and brightness are maintained, and high-quality clear image quality can be expressed.

Claims (4)

A self-luminous photosensitive resin composition for a color filter pixel, which comprises a quantum dot, an alkali-soluble resin having a repeating unit represented by the following chemical formula 1 in a molecular structure, a photopolymerizable compound, and a photopolymerization initiator: In the chemical formula 1, R ₁ is hydrogen or methyl, and R ₂ is an alkyl group of C1 to C30, an alkyloxy group of C1 to C30, or an alkyloxycarbonylaminoalkyl group of C3 to C30, wherein, the Alkyl, alkyloxy or alkyloxycarbonylaminoalkyl can be C1-C20 alkyl, C1-C20 alkoxy, C6-C20 aralkyl, C6-C20 aryl, C2 ~ C20 fluorenyl group, C2 ~ C20 fluorenyl group, C2 ~ C20 alkoxycarbonyl group, C7 ~ C20 arylcarbonyl group, C2 ~ C20 dialkylamino group, C1 ~ C20 alkylamine group, Halogen atom, cyano, furyl, furfuryl, tetrahydrofuranyl, tetrahydrofurfuryl, C1-C20 alkylthio, trimethylsilyl, trifluoromethyl, carboxyl, thienyl, morpholinyl Or morpholino carbonyl, R _{3 is} represented by -R ₅ -R ₆ -COOH, where R ₅ is -OC (= O)-, and R ₆ contains C1-C30 alkylene and C2-C30 alkylene Base, -R ₇ -C (= O) -R _8- , -R ₉ -C (= O) -OR _10- , -R ₁₁ -OR _12- , -R ₁₃ -C (= O) -N- (R ₁₄ R ₁₅ )-, -RC (= O) -NR ₁₆ -C (= O) R _17- , -R ₁₈ -C (= O) -N (R ₁₉ ) (C (= O))- R _20- , -R ₂₁ -C (= NR ₂₂ ) (R ₂₃ )-, -CH = CH-OC (= O) -R _24- , -CH = CH-OCR _25- , -CH = CH-OC (= O) -N (R ₂₆ ) (R ₂₇ )-, C6 ~ C30 Aryl, C5 ~ C30 heteroaryl, C6 ~ C30 cycloalkyl, wherein R ₇ to R ₂₇ are the same or different from each other, and are each independently hydrogen, C1 ~ C30 alkyl, C6 ~ C30 extended aryl group or C6 ~ C30 extended cycloalkyl group, where R ₆ can pass through C1 ~ C20 alkyl group, C1 ~ C20 alkoxy group, C6 ~ C20 arylalkyl group, C6 ~ C20 aromatic group Group, fluorenyl group of C2 to C20, fluorenyl group of C2 to C20, alkoxycarbonyl group of C2 to C20, arylcarbonyl group of C7 to C20, dialkylamino group of C2 to C20, alkyl group of C1 to C20 Amine group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, C1-C20 alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl group, thienyl group, etc. It is substituted by a phosphono group or a morpholino carbonyl group, R ₄ is an alkyl (meth) acrylate group of C4 to C20, and the self-luminous photosensitive resin composition includes 100% by weight of the entire composition: quantum The point is 3 to 80% by weight, the alkali-soluble resin is 5 to 80% by weight, the photopolymerizable compound is 5 to 70% by weight, and the photopolymerization initiator is 0.1 to 20% by weight. The self-luminous photosensitive resin composition for a color filter pixel of claim 1, wherein R ₂ is a C1-C20 alkyl group, a C1-C20 alkyloxy group, or a C3-C20 alkyloxy group. Carbonylaminoalkyl, R _{3 is} represented by -R ₅ -R ₆ -COOH, where R ₅ is -OC (= O)-, R ₆ is an alkylene group of C1 ~ C20, and an alkylene group of C2 ~ C20 , C6 ~ C20 extended aryl or C6 ~ C20 extended cycloalkyl, which may be substituted by carboxyl or unsubstituted, R ₄ is C4 ~ C12 (meth) acrylic acid alkyl ester group. A color filter manufactured from a self-luminous photosensitive resin composition for a color filter pixel of claim 1 or 2. An image display device includes a color filter according to claim 3.