JP2016157114A - Curable composition comprising quantum dots, and color filter and image display device produced using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition comprising quantum dots which allow production of an excellent color filter while uniformly dispersing quantum dot particles without problems such as light efficiency degradation and impaired photosensitive properties during a production process of the color filter.SOLUTION: The present invention provides a color filter produced from such a curable composition comprising quantum dots, and an image display device comprising the same.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition containing quantum dots, a color filter produced using the same, and an image display device.

  The color filter is a thin film type optical component that extracts three kinds of colors of red, green, and blue from white light and enables a fine pixel unit. The size of one pixel is several tens to several hundreds. It is about a micrometer. Such a color filter has a black matrix layer formed in a pattern defined on a transparent substrate in order to shield a boundary portion between each pixel and a plurality of colors (usually red) to form each pixel. (R), green (G), and blue (B)) have a structure in which pixel portions arranged in a predetermined procedure are sequentially stacked. Generally, a color filter can be manufactured by coating three or more hues on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. The pigment dispersion method using a photosensitive resin is the mainstream.

  A pigment dispersion method, which is one of the methods for embodying a color filter, includes a colorant on a transparent substrate provided with a black matrix, an alkali-soluble resin, a photopolymerization monomer, a photopolymerization initiator, After coating a photosensitive resin composition containing an epoxy resin, solvent, and other additives, exposing the pattern in the form to be formed, removing the non-exposed areas with a solvent and repeating the process of thermosetting The method of forming a colored thin film is actively applied to manufacture LCDs for mobile phones, notebook computers, monitors, televisions, and the like. In recent years, even in photosensitive resin compositions for color filters using a pigment dispersion method having various advantages, not only excellent pattern characteristics, but also high performance such as high luminance and high contrast ratio as well as high color reproduction ratio. What is required is the current situation.

  However, the color reproduction is realized by the light emitted from the light source being transmitted through the color filter, but in this process, part of the light is absorbed by the color filter, so the light efficiency decreases, In addition, there is a fundamental limitation that perfect color reproduction is insufficient due to the pigment characteristics as a color filter.

  Patent Document 1 includes a light source and a display panel on which light emitted from the light source is incident. The display panel includes a number of color conversion units, and the color conversion unit A display device is disclosed that includes a large number of wavelength converting particles that convert wavelengths and a large number of color filter particles that absorb light in a predetermined wavelength band with the light.

  However, the prior art is similar in that quantum dots are included, but there is no specific explanation for the content of the photosensitive resin composition, and only a display device having a high color reproduction rate and brightness is disclosed. Therefore, additional development for the photosensitive resin composition is necessary.

Korean Patent Publication No. 10-2013-0000506

  The present invention is a curable composition comprising quantum dots that can produce excellent color filters without causing problems such as a decrease in light efficiency and poor photosensitivity during the color filter production process while uniformly dispersing the quantum dot particles. An object is to provide a composition.

  Moreover, an object of this invention is to provide the color filter manufactured with the curable composition containing such a quantum dot, and an image display apparatus containing the same.

  In order to achieve the above object, the curable composition including quantum dots according to an embodiment of the present invention includes a binder and quantum dots, and the binder includes one or more of the following chemical formula 1, chemical formula 2, and combinations thereof.

[Chemical Formula 1]

(In Formula 1 above,
R ₁ represents hydrogen or a C1-C6 alkyl group,
R ₂ represents oxygen, —NH— or

Group,
R ₃ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group,
R ₄ represents a group containing an unsaturated double bond. )

[Chemical formula 2]

(In Formula 2 above,
R _{5 to} R ₆ are each independently the same or different and each represents hydrogen or a C1-C6 alkyl group;
R ₇ is oxygen, —NH— or

Group,
R ₈ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group,
R ₉ represents a group containing an unsaturated double bond,
X represents a value of 0 <X <100. )

  As described above, the curable composition containing the quantum dots according to the present invention has an effect of providing a high-quality color filter excellent in color reproducibility and luminance characteristics by including a specific compound binder.

  Moreover, this invention has the effect which can provide the color filter manufactured with the curable composition containing the said quantum dot, and an image display apparatus containing this.

  The curable composition comprising quantum dots according to the present invention comprises a binder and quantum dots, wherein the binder is represented by the following chemical formula 1 or chemical formula 2.

  In addition, the curable composition containing the quantum dots of the present invention, together with the binder and quantum dots, has one o-naphthoquinonediazide compound when the positive type is used, and one when the negative type is used. A monomer or oligomer having the above ethylenically unsaturated group and a photopolymerization initiator may be further contained. You may further contain other components, such as a crosslinking agent, as needed. Moreover, when comprised by the said positive type | mold, the said monomer or oligomer and a photoinitiator can further be included.

  First, the curable composition including the quantum dots of the present invention may include a binder of Chemical Formula 1, and a glass transition temperature may be -20 to 250 ° C. In this case, the binder is a copolymer having a polymerizable side chain.

[Chemical Formula 1]

In Formula 1,
R ₁ represents hydrogen or a C1-C6 alkyl group. More preferably, R ₁ can be freely selected in consideration of film strength, elastic modulus, viscoelasticity, heat resistance, developability, glass transition temperature (Tg) of polymer, solubility, suitability for synthesis, and the like.

R ₂ represents oxygen, —NH— or

Indicates a group. More preferably, R ₂ can be freely selected in consideration of film strength, elastic modulus, viscoelasticity, heat resistance, developability, synthesis suitability, polymer glass transition temperature (Tg), solubility, and the like.

R ₃ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group. R ₃ is preferably a C1 to C25 alkylene group, a C1 to C25 alkyleneoxy group or a C1 to C25 ethyloxycarbonylaminoethyl group, a C1 to C20 alkylene group, a C1 to C20 alkyloxy group or a C1 to C20. The ethyloxycarbonylaminoethyl group is more preferably methylene group, ethylene group, propylene group, butylene group, ethyleneoxy group, diethyleneoxy group, triethyleneoxy group, and ethyloxycarbonylaminoethyl group. These groups may have a substituent. In this case, the substituent of R ₃ is preferably a C1-C20 alkyl group, more preferably a C1-C15 alkyl group, still more preferably a C1-C10 alkyl group, and a C1-C7 alkyl group. Particularly preferred. Specifically, considering the raw materials and suitability for synthesis, the substituent is most preferably a methyl group, an ethyl group, a branched or straight chain propyl group, a butyl group, a pentyl group, and a hexyl group. However, alcoholic hydroxyl groups are excluded from the preferred examples because they may lower the glass transition temperature (Tg).

R ₄ represents a group containing an unsaturated double bond. Specifically, a vinyloxy group, an allyloxy group, a (meth) acryloyloxy group, a 4-vinylphenyloxy group, a 4-vinylphenylmethyloxy group, a vinyl ester group, and the like are preferable. Among them, as R ₄ , a vinyloxy group, an allyloxy group, a (meth) acryloyloxy group, a 4-vinylphenylmethyloxy group, and a vinyl ester group are more preferable, and an allyloxy group, a (meth) acryloyloxy group, and 4-vinylphenylmethyl. An oxy group is particularly preferred.

  The glass transition temperature (Tg) of the binder in the present invention containing the structural unit represented by Chemical Formula 1 can be adjusted by the molecular weight of the binder itself, the molecular structure, the use of hydrogen bonding interaction, and the like. It is determined in consideration of the glass transition temperature (Tg), the affinity with the binder used together and other components, the viscoelasticity of the entire system, and the like. When the glass transition temperature (Tg) of the binder is excessively low, the heat resistance of the formed pattern is lowered, and problems such as heat flow occur. In addition, problems such as increased adhesiveness of the coating film and reduced workability occur. For this reason, it is not preferable to contain an alcoholic hydroxyl group in the binder. In addition, since alcoholic hydroxyl groups have relatively weak hydrogen bonding interactions, there are many cases where a large effect cannot be exhibited from this viewpoint.

  The glass transition temperature (Tg) of the binder in the present invention is preferably in the range of -20 to 250 ° C, more preferably in the range of -15 to 250 ° C, and in the range of -10 to 250 ° C. Is particularly preferred. Moreover, you may use the binder in this invention together with another binder. In addition, binders other than those described above will be described later.

  The molecular weight of the binder in the present invention is a weight average molecular weight, preferably 500 to 10,000,000 Da (dalton: unit of molecular weight), more preferably 1,000 to 5,000,000 Da, and 2,000. ˜5,000,000 Da is particularly preferred.

  The component (that is, copolymerization component) constituting the binder in the present invention together with the structural unit represented by Chemical Formula 1 is not particularly limited as long as copolymerization (two or more) is possible.

  Examples of the copolymer component include, for example, JP-A 59-44615, JP-B 54-34327, JP-B 58-12777, JP-B 54-25957, and JP Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer as described in the specifications of JP-A-59-53836 and JP-A-59-71048, (Anhydrous) Maleic acid copolymer, Partially esterified maleic acid copolymer, Monomer used in partially amidated maleic acid copolymer, (Meth) acrylates, (Meth) acrylamides, Fragrance with vinyl group Aromatic hydrocarbon rings, heteroaromatic rings having a vinyl group, maleic anhydride, itaconic acid esters, crotonic acid esters, (meth) acrylonitrile, (meth ) Crotononitrile, various styrenes, various benzoyloxy ethylenes, various acetoxy ethylene, vinyl carbazole, vinyl pyrrolidone, and the like are exemplified.

  Among these, as the copolymer component, (meth) acrylic acid, C1-C25 (cyclo) alkyl (meth) acrylate, (meth) acrylate having a C1-C25 bicyclo ring, C1-C25 aralkyl (meth) ) Acrylate, C1-C25 aryl (meth) acrylate, (meth) acrylamide, C1-C25 secondary or tertiary (cyclo) alkyl (meth) acrylamide, C1-C25 secondary or tertiary bicyclo ring. (Meth) acrylamide having C1 to C25 secondary or tertiary aralkyl (meth) acrylamide, C1 to C25 secondary or tertiary aryl (meth) acrylamide, C1 to C25 (meth) acryloylmorpholine, vinyl group A substituted or unsubstituted C1-C25 aromatic hydrocarbon ring having Substituted or unsubstituted carbon C1-C25 heteroaromatic ring having an alkyl group, maleic anhydride, substituted or unsubstituted C1-C25 (α-methyl-) styrene, vinylimidazole, vinyltriazole, maleic anhydride, Substituted or unsubstituted C1-C25 partially esterified maleic acid copolymer, substituted or unsubstituted C1-C25 partially amidated maleic acid, methyl jasmonate, itaconic acid, C1-C25 itacone Acid (cyclo) alkyl ester, itaconic acid ester having C1-C25 bicyclo ring, C1-C25 itaconic acid aralkyl ester, C1-C25 itaconic acid aryl ester, crotonic acid, C1-C25 crotonic acid (cyclo) alkyl Ester, C1-C25 Bisshi Crotonic acid ester having B-ring, C1-C25 crotonic acid aralkyl ester, C1-C25 crotonic acid aryl ester, C1-C25 benzoyloxyethylenes, C1-C25 acetoxyethylenes, (meth) acrylonitrile, (meta ) Crotonnitrile, C1-C25 vinyl carbazole and vinyl pyrrolidone are preferred.

  Among these, (meth) acrylic acid, C1-C20 (cyclo) alkyl (meth) acrylate, C1-C20 bicyclo ring (meth) acrylate, C1-C20 aralkyl (meth) acrylate, C1-C20 Aryl (meth) acrylate, (meth) acrylamide, C1-C20 secondary or tertiary (cyclo) alkyl (meth) acrylamide, C1-C20 secondary or tertiary bicyclo ring (meth) acrylamide, C1 -C20 secondary or tertiary aralkyl (meth) acrylamide, C1-C20 secondary or tertiary aryl (meth) acrylamide; C1-C20 (meth) acryloylmorpholine, substituted or unsubstituted with a vinyl group C1-C20 aromatic hydrocarbon ring, substituted or substituted with vinyl group Unsubstituted C1-C20 heteroaromatic ring, maleic anhydride, substituted or unsubstituted C1-C20 partially esterified maleic acid copolymer, substituted or unsubstituted C1-C20 partially amidated maleic acid, substituted Or unsubstituted C1-C20 (α-methyl-) styrenes, methyl jasmonate, itaconic acid, C1-C20 itaconic acid (cyclo) alkyl ester, C1-C20 itaconic acid ester having a bicyclo ring, C1 ~ C20 itaconic acid aralkyl ester, C1 ~ C20 itaconic acid aryl ester, crotonic acid, C1 ~ C20 crotonic acid (cyclo) alkyl ester, C1 ~ C20 crotonic acid ester having bicyclo ring, C1 ~ C20 crotonic acid Aralkyl ester, C1-C20 crotonic acid aryl ester C1-C20 benzoyloxyethylenes, C1-C20 acetoxyethylenes, C1-C20 vinylcarbazole, vinylpyrrolidone; (meth) acrylonitrile, (meth) crotononitrile are more preferred.

  Of these, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, linear or branched propyl (meth) acrylate, linear or branched butyl (meth) acrylate, linear or branched Pentyl (meth) acrylate, normal hexyl (meth) acrylate, cyclohexyl (meth) acrylate, normal heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, normal octyl (meth) acrylate, normal decyl (meth) acrylate, normal Dodecyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, norbornanemethyl (meth) acrylate, norbornenemethyl (meth) acrylate; benzyl (meth) acrylate , Naphthylmethyl (meth) acrylate, anthracenemethyl (meth) acrylate, phenylethyl (meth) acrylate; phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylamide, (di) methyl (meth) acrylamide, (Di) ethyl (meth) acrylamide, linear or branched (di) propyl (meth) acrylamide, linear or branched (di) butyl (meth) acrylamide, linear or branched (di) pentyl (meth) acrylamide , (Di) normal hexyl (meth) acrylamide, (di) cyclohexyl (meth) acrylamide, (di-) 2-ethylhexyl (meth) acrylamide; adamantyl (meth) acrylamide, noradamantyl (meth) acrylamide; benzyl (meth) Acrylamide, naphthylethyl (meth) acrylamide, phenylethyl (meth) acrylamide; (di) phenyl (meth) acrylamide, naphthyl (meth) acrylamide, (meth) acryloylmorpholine, piperidylacrylamide, pyrrolidylacrylamide, (α-methyl) styrene , Vinylpyridine, vinylimidazole, vinyltriazole, maleic anhydride, methyl jasmonate; itaconic acid; crotonic acid, methyl crotonate, ethyl crotonate, linear or branched propyl crotonate, linear or branched butyl crotonate , Linear or branched pentyl crotonate, normal hexyl crotonate, cyclohexyl crotonate, normal heptyl crotonate, 2-ethylhexyl crotonate, normal Octyl crotonate, normal decyl crotonate, normal dodecyl crotonate; adamantyl crotonate, isobornyl crotonate, norbornane methyl crotonate, norbornene methyl crotonate; benzyl crotonate, naphthyl methyl crotonate, anthracene methyl crotonate, phenylethyl Crotonate; phenylcrotonate, naphthylcrotonate, benzoyloxyethylene, acetoxyethylene, vinylcarbazole, vinylpyrrolidone and the like are particularly preferable.

  The carboxyl group may be made of a metal salt.

  Examples of the substituent include a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C1 to C20 aralkyl group, a C1 to C20 aryl group, a C1 to C20 acyloxy group, a C1 to C20 acyl group, and a C1 to C20 acyl group. C20 alkoxycarbonyl group, C1-C20 arylcarbonyl group, C1-C20 dialkylamino group, C1-C20 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfuryl group An alkylthio group, a trimethylsilyl group, a trifluoromethyl group, a carboxyl group, a thienyl group, a morpholino group, a morpholinocarbonyl group, and the like are preferable.

  Among these, the substituent includes a C1-C15 alkyl group, a C1-C15 alkoxy group, a C1-C15 aralkyl group, a C1-C15 aryl group, a C1-C15 acyloxy group, and a C1-C15 acyl group. Group, C1-C15 alkoxycarbonyl group, C1-C15 arylcarbonyl group, C1-C15 dialkylamino group, C1-C15 alkylamino group, halogen atom, cyano group, furyl group, furfuryl group, tetrahydrofuryl group, A tetrahydrofurfuryl group, an alkylthio group, a trimethylsilyl group, a trifluoromethyl group, a carboxyl group, a thienyl group, a morpholino group, a morpholinocarbonyl group and the like are more preferable.

  Examples of the substituent include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, a normal hexyl group, a cyclohexyl group, a normal heptyl group, 2 -Ethylhexyl group, normal octyl group, normal decyl group, normal dodecyl group, methyloxy group, ethyloxy group, linear or branched propyloxy group, linear or branched butyloxy group, linear or branched pentyloxy group, normal Hexyloxy group, cyclohexyloxy group, normal heptyloxy group, 2-ethylhexyloxy group, normal octyloxy group, normal decyloxy group, normal dodecyloxy group, benzyl group, penetyl group, naphthylmethyl group, naphthylethyl group, phenyl group , Naphthyl group, meth A carbonyloxy group, an ethylcarbonyloxy group, a linear or branched propylcarbonyloxy group, a linear or branched butylcarbonyloxy group, a linear or branched pentylcarbonyloxy group, a normal hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, Normal heptylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, normal octylcarbonyloxy group, normal decylcarbonyloxy group, normal dodecylcarbonyloxy group, methylcarbonyl group (acetyl group), ethylcarbonyl group, linear or branched propylcarbonyl Group, linear or branched butylcarbonyl group, linear or branched pentylcarbonyl group, normal hexylcarbonyl group, cyclohexylcarbonyl group, normal heptyl Carbonyl group, 2-ethylhexylcarbonyl group, normal octylcarbonyl group, normal decylcarbonyl group, normal dodecylcarbonyl group, methyloxycarbonyl group, ethyloxycarbonyl group, linear or branched propyloxycarbonyl group, linear or branched butyl Oxycarbonyl group, linear or branched pentyloxycarbonyl group, normal hexyloxycarbonyl group, cyclohexyloxycarbonyl group, normal heptyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, normal octyloxycarbonyl group, normal decyloxycarbonyl group, Normal dodecyloxycarbonyl group, benzoyl group, naphthylcarbonyl group; (di) methylamino group, (di) ethylamino group, linear or branched (di ) Propylamino group, linear or branched (di) butylamino group, linear or branched (di) pentylamino group, (di) normal hexylamino group, (di) cyclohexylamino group, (di) normal heptylamino Group, (di) 2-ethylhexylamino group; fluorine atom, chlorine atom, bromine atom; cyano group, furyl group, furfuryl group, tetrahydrofuryl group, tetrahydrofurfuryl group, alkylthio group, trimethylsilyl group, trifluoromethyl group, carboxyl A group, a thienyl group, a morpholino group, a morpholinocarbonyl group and the like are particularly preferable.

  Further, these substituents may be further substituted with the above-described substituents. However, alcoholic hydroxyl groups are excluded from the preferred substituent examples because they may lower the glass transition temperature (Tg).

  In addition, (meth) acrylonitrile and (meth) crotononitrile are examples of particularly preferable copolymerization components (copolymerization monomers).

  As the copolymer component, monomers having other hydrophilic properties such as phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, etc. Etc. are useful.

  The sulfonic acid group and carboxylic acid group may be made of a metal salt.

  In the binder of the present invention, the type and number of monomers to be copolymerized are not particularly limited, but 1 to 12 types are preferable, 1 to 8 types are more preferable, and 1 to 5 types are particularly preferable.

  Hereinafter, although the specific example of the binder in the form of Chemical formula 1 of this invention is shown by Chemical formula 1-1-Chemical formula 1-24, this invention is not limited to these.

[Chemical Formula 1-1]
Glass transition temperature (Tg) = 120 ° C.

[Chemical formula 1-2]
Glass transition temperature (Tg) = 130 ° C.

[Chemical formula 1-3]
Glass transition temperature (Tg) = 160 ° C.

[Chemical formula 1-4]
Glass transition temperature (Tg) = 160 ° C.

[Chemical formula 1-5]
Glass transition temperature (Tg) = 135 ° C.

[Chemical formula 1-6]
Glass transition temperature (Tg) = 150 ° C.

[Chemical formula 1-7]
Glass transition temperature (Tg) = − 1.3 ° C.

[Chemical formula 1-8]
Glass transition temperature (Tg) = − 19.3 ° C.

[Chemical formula 1-9]
Glass transition temperature (Tg) = 120 ° C.

[Chemical formula 1-10]
Glass transition temperature (Tg) = 130 ° C.

[Chemical formula 1-11]
Glass transition temperature (Tg) = 140 ° C.

[Chemical formula 1-12]
Glass transition temperature (Tg) = 140 ° C.

[Chemical formula 1-13]
Glass transition temperature (Tg) = 160 ° C.

[Chemical formula 1-14]
Glass transition temperature (Tg) = 130 ° C.

[Chemical formula 1-15]
Glass transition temperature (Tg) = 140 ° C.

[Chemical formula 1-16]
Glass transition temperature (Tg) = 140 ° C.

[Chemical formula 1-17]
Glass transition temperature (Tg) = 150 ° C.

[Chemical formula 1-18]
Glass transition temperature (Tg) = 140 ° C.

[Chemical formula 1-19]
Glass transition temperature (Tg) = 130 ° C.

[Chemical formula 1-20]
Glass transition temperature (Tg) = 120 ° C.

[Chemical formula 1-21]
Glass transition temperature (Tg) = 120 ° C.

[Chemical formula 1-22]
Glass transition temperature (Tg) = 130 ° C.

[Chemical formula 1-23]
Glass transition temperature (Tg) = 160 ° C.

[Chemical formula 1-24]
Glass transition temperature (Tg) = 120 ° C.

  Next, the curable composition containing the quantum dots of the present invention may include a binder of Formula 2, and may have a glass transition temperature of -20 to 250 ° C.

  By containing the compound represented by Chemical Formula 2, curability at the time of light (radiation) irradiation can be improved, and a pattern having a high degree of curing can be formed. Therefore, it has high resolution and can exhibit excellent luminance characteristics by acting as a protecting group from the radicals generated during the POB process to the surface of the quantum dots.

[Chemical formula 2]

In Formula 2, R ₅ and R ₆ are each independently the same or different and represent hydrogen or a C1-C6 alkyl group.

R ₇ is oxygen, —NH— or

Indicates a group.

R ₈ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group.

Alkylene group represented by R _8, alkyleneoxy group, and among the ethyloxycarbonyl aminoethyl group, both preferably having C1～C25, more preferably those of C1 to C20, methylene group, ethylene group, propylene Group, butylene group, ethyleneoxy group, diethyleneoxy group, triethyleneoxy group, and ethyloxycarbonylaminoethyl group are particularly preferred. These groups may have a substituent. The substituent for R ₈ is preferably a C1-C20 alkyl group or OH group, more preferably a C1-C15 alkyl group or OH group, more preferably a C1-C10 alkyl group or OH group, and C1. A C7 alkyl group or an OH group is particularly preferred. Among these, in view of raw materials and synthesis suitability, a methyl group, an ethyl group, a branched or linear propyl group, a butyl group, a pentyl group, a hexyl group, and an OH group are most preferable.

R ₉ represents a group containing an unsaturated double bond.

R ₉ represents a group containing an unsaturated double bond, vinyloxy group, allyloxy group, (meth) acryloyloxy group, 4-vinylphenyloxy group, 4-vinylphenylmethyloxy group, styryl group, vinyl ester. Groups selected from the group consisting of groups and vinyl ether groups are preferred. Among them, vinyloxy group, allyloxy group, (meth) acryloyloxy group, 4-vinylphenylmethyloxy group, and vinyl ester group are more preferable, and allyloxy group, (meth) acryloyloxy group, and 4-vinylphenylmethyloxy group are particularly preferable. .

  X represents a value of 0 <X <100. More preferably, X represents film strength, elastic modulus, viscoelasticity, heat resistance, synthesis suitability, polymer glass transition temperature (Tg), solubility, developability, synthesis suitability, film developability, developer concentration. , And can be appropriately selected in consideration of the interaction strength with the quantum dots and other components. Among them, X is preferably a value of 5 to 95, more preferably a value of 10 to 90, and particularly preferably a value of 15 to 85.

  The molecular weight of the compound represented by Chemical Formula 2 is preferably a weight average molecular weight of 500 to 10,000,000 Da (Dalton: unit of molecular weight), more preferably 100 to 5,000,000 Da, and 2,000 to 5,000,000 Da is particularly preferred.

  The binder is particularly preferably water-soluble or alkali-soluble. Here, alkali-soluble means that it is soluble in an aqueous solution of the following alkaline compound or a mixture of these with an organic solvent miscible with water.

  Hereinafter, although the specific example of the compound represented by said Chemical formula 2 is enumerated, this invention is not limited to these.

  10-90 mass% is preferable with respect to the total solid content (mass) of the curable composition containing a quantum dot, and the binder containing the compound represented by the said Chemical formula 1 or Chemical formula 2 is more preferable 15-80 mass%. .

  If the content of the binder is less than the above range, the effect of improving the degree of curing by irradiation with light (radiation) is insufficient, and the heat resistance, resolution, remaining film ratio of the cured part, developability of the uncured part, etc. are effective. May decrease. On the other hand, if the above range is exceeded, the content of other components may be excessively lowered, and developability and colorability may be damaged.

  The curable resin composition of the present invention includes photoluminescent quantum dot particles.

  Quantum dots are nano-sized semiconductor materials. When atoms form molecules, and molecules are small, called clusters, they form an assembly of molecules and form nanoparticles. When such nanoparticles have semiconductor characteristics, they are called quantum dots. When the quantum dot is lifted by receiving energy from the outside, the quantum dot releases energy by its own energy band gap.

  The curable composition of the present invention contains such photoluminescent quantum dot particles, and a color filter produced therefrom can emit light (photoluminescence) by irradiation with light. In a normal image display device including a color filter, white light is transmitted through the color filter to realize a color. In this process, a part of the light is absorbed by the color filter, so that the light efficiency is lowered. However, when the color filter manufactured with the curable composition of the present invention is included, the color filter emits itself by the light of the light source, so that excellent light efficiency can be realized. In addition, since light having a hue is emitted, the color reproducibility is excellent, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

  The quantum dot particle according to the present invention is not particularly limited as long as it is a quantum dot particle that can emit light when stimulated by light. For example, a II-VI group semiconductor compound; a III-V group semiconductor compound; a IV-VI group semiconductor compound; A compound comprising the same; and combinations thereof. These can be used alone or in admixture of two or more. The II-VI group semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS 3dCe, selected from the group consisting of ZnO, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HdZnS, HgZnSe, HgZnTe, and mixtures thereof; Four elements selected from the group consisting of CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof The group III-V semiconductor compound may be selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. A binary element selected from the group consisting of: GNP, GNAs, GNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof Ternary compounds; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNS , InAlPAs, InAlPSb, and a mixture thereof. The IV-VI semiconductor compound may be selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and the like. Two elemental compounds selected from the group consisting of these mixtures; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe and three elemental compounds selected from the mixture thereof; and SnPbSSe, SnPbSe , SnPbSTe and a group consisting of quaternary compounds selected from the group consisting of these, wherein the group IV element or the compound containing it is selected from the group consisting of Si, Ge, and mixtures thereof Selected And an elemental compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

  Quantum dot particles can be a homogenous single structure; a double structure such as a core-shell, a gradient structure, etc .; or a mixed structure thereof. The core-shell dual structure and the core and shell materials may be composed of the above-mentioned different semiconductor compounds. For example, the core may include one or more materials selected from the group consisting of, but not limited to, CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO. is not. The shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto. Photoluminescent quantum dot particles, such as red, green, and blue colorants used for the production of ordinary color filters, include red, green, and blue colorants for the purpose of hue. The quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles, or blue quantum dot particles.

  Quantum dot particles can be synthesized by a wet chemical process, a metal organic chemical vapor deposition process or a molecular beam epitaxy process. The wet chemical process is a method of growing particles by putting a precursor substance in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to regulate the growth of the crystal, so metal organic chemical vapor deposition (MOCVD) In addition, the growth of nanoparticles can be controlled through a process that is easier and less expensive than vapor deposition such as molecular beam epitaxy (MBE).

  The content of the quantum dot particles according to the present invention is not particularly limited. For example, the content is preferably 3 to 80% by weight, and preferably 5 to 70% by weight, based on the total solid content of the photosensitive resin composition. Is more preferable. If the content of the quantum dot particles is less than the above range, the light emission efficiency is very weak. If the content exceeds the above range, the content of other compositions is relatively insufficient, and it is difficult to form a pixel pattern.

  The curable composition containing the quantum dot of the present invention may further contain another binder that can be used in combination with the compound represented by Chemical Formula 1 or Chemical Formula 2.

  Other binders are not particularly limited as long as they are alkali-soluble, but are preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer described in Japanese Patent Publication No. 54-25957, Japanese Unexamined Patent Publication No. 59-53836, Japanese Unexamined Patent Publication No. 59-71048. Polymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., and acidic cellulose derivatives having a carboxylic acid in the side chain are used.

  In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  Further, in the first embodiment, a binder composed of components (that is, copolymerization components) constituting the binder in the present invention is usefully used together with the structural unit represented by the chemical formula 1 described above.

  Moreover, what copolymerized the monomer which has hydrophilic property may be sufficient, for example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, etc. Group, phosphoric acid, phosphoric acid esters, quaternary ammonium salts, ethyloxy chain, a propyleneoxy chain, sulfonic acid and its salts, monomers containing a morpholinoethyl group.

  In the first embodiment, the glass transition temperature (Tg) containing the structural unit represented by Chemical Formula 1 is in the range of −20 to 250 ° C., and the other binder used in combination with the binder in the present invention is the viscosity of the system. In the case where the elasticity and glass transition temperature (Tg) can be maintained in a desired range, an alcoholic hydroxyl group may be contained.

  Further, in the present invention, from the viewpoint of improving the crosslinking efficiency, the polymer may have a polymerizable group in the side chain, an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain. Is also useful. Examples of the polymer having a polymerizable group in the side chain include KS resist-106 (product of Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (product of Daicel Chemical Industries, Ltd.) and the like.

  From the viewpoint of further improving the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Of these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. A resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable. Moreover, when used with the binder of the 1st viewpoint, the binder which consists of a component (namely, copolymerization component) which comprises a high molecular compound with the structural unit represented by Chemical formula 1 is preferable.

  Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and KS resist-106 (Osaka Organic Chemical). Kogyo Co., Ltd. product), cyclomer P series and the like are preferable.

  Alkali-soluble phenol resins are also useful. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.

  Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, bisphenol A, and the like. These phenols can be used alone or in a combination of two or more. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like.

  Specific examples of the novolak resin include a condensation product of metacresol, paracresol or a mixture thereof and formalin. The molecular weight distribution of these novolak resins may be adjusted using a means such as fractionation. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C or bisphenol A, in the said novolak resin.

  The weight average molecular weight (polystyrene conversion value measured by GPC method) of the other binder is preferably 500 to 10,000,000 Da (Dalton: unit of molecular weight), more preferably 1,000 to 5,000,000 Da. 2,000 to 5,000,000 Da is preferable.

  The other binder is used in combination with the binder in the present invention, and may not be used if the performance can be sufficiently exhibited by using only the binder in the present invention.

  Moreover, when using together the binder represented by Chemical formula 1 or Chemical formula 2 in this invention and another binder, the usage-amount in the curable composition containing the quantum dot of this invention of the said other binder is the amount in a composition. 0-90 mass% is preferable with respect to the total solid content, 0-80 mass% is more preferable, and 0-70 mass% is especially preferable.

  The curable composition containing the quantum dots of the present invention can further contain a crosslinking agent so as to obtain a film cured with higher sensitivity.

  The crosslinking agent that can be used in the present invention is not particularly limited as long as the film is cured by a crosslinking reaction, and is selected from, for example, an epoxy resin (a), a methylol group (b), an alkoxymethyl group, and an acyloxymethyl group. Substituted with one or more substituents selected from melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, methylol groups (c), alkoxymethyl groups, and acyloxymethyl groups substituted with one or more substituents Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, multi-sensitive epoxy resins are preferred.

  The cross-linking agent (a) may be any one having an epoxy group and a cross-linking property. For example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diester Divalent glycidyl group-containing low molecular weight compounds such as glycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline, trimethylolpropane triglycidyl ether, trimethylolphenol tri Trivalent glycidyl group-containing low molecular weight compounds represented by glycidyl ether, TrisP-PA triglycidyl ether, etc., in the same form, pentaerythritol tetraglycidyl ether, tetramethylol bis Tetravalent glycidyl group-containing low molecular weight compounds represented by enol A tetraglycidyl ether, etc., polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether in the same form, Polyglycidyl (meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct, etc. Can be.

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6, in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. 2 to 4, preferably 5 to 6 in the case of a melamine compound, and 3 to 4 in the case of a glycoluril compound, a guanamine compound and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of the crosslinking agent (b) are generally referred to as compounds (containing methylol group, alkoxymethyl group or acyloxymethyl group) relating to the crosslinking agent (b).

  The methylol group-containing compound relating to the crosslinking agent (b) is obtained by heating the alkoxymethyl group-containing compound relating to the crosslinking agent (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid or methanesulfonic acid. can get. The acyloxymethyl group-containing compound relating to the crosslinking agent (b) can be obtained by mixing and stirring the methylol group-containing compound relating to the crosslinking agent (b) with an acyl chloride in the presence of a basic catalyst.

  Hereinafter, specific examples of the compound relating to the crosslinking agent (b) having the substituent are listed.

  Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol guanamine. Or a compound obtained by acyloxymethylating 1 to 3 methylol groups, or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

  Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.

  These compounds relating to the crosslinking agent (b) may be used alone or in combination. The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with one or more groups selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case, it suppresses intermixing with the photoresist overcoated by thermal crosslinking and further increases the film strength. Hereinafter, these compounds may be generally referred to as methylol group, alkoxymethyl group or acyloxymethyl group-containing compound related to the crosslinking agent (c).

  The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the cross-linking agent (c) must be at least 2 per molecule, and it becomes a skeleton from the viewpoint of thermal crosslinkability and storage stability. Compounds in which the 2-position and 4-position of the phenol compound are all substituted are preferred. Further, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho position and para position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent. Also in the naphthol compound, except for the ortho position of the OH group, it may be unsubstituted or may have a substituent.

  The methylol group-containing compound related to the crosslinking agent (c) is a compound in which the phenolic OH group is a hydrogen atom at the 2-position or 4-position, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium. It can be obtained by reacting with formalin in the presence of a basic catalyst such as hydroxide.

  The alkoxymethyl group-containing compound relating to the crosslinking agent (c) is obtained by heating the methylol group-containing compound relating to the crosslinking agent (c) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid in alcohol. can get.

  The acyloxymethyl group-containing compound relating to the crosslinking agent (c) can be obtained by reacting the methylol group-containing compound relating to the crosslinking agent (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include phenol compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, naphthol, hydroxyanthracene compounds, and the like, for example, phenol, cresol isomers, 2, 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisPPA (product of Honshu Chemical Industry Co., Ltd.), naphthol, Dihydroxynaphthalene, 2,7-dihydroxyanthracene and the like are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating 1 to 2 methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4, 4′-bishydroxybiphenyl, tetramethoxymethyl-4, 4 ′ Bishydroxybiphenyl, TrisP-PA hexamethylol body, TrisP-PA hexamethoxymethyl body, TrisP-PA hexamethylol body compound having 1 to 5 methylol groups methoxymethylated, Bishydroxymethylnaphthalenediol, etc. Can be.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and the acyloxymethyl group-containing compound includes, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

  Among these compounds, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, TrisP-PA (product of Honshu Chemical Industry Co., Ltd.) hexamethylol or their methylol group is an alkoxymethyl group. And a phenol compound substituted with both a methylol group and an alkoxymethyl group.

  These compounds relating to the crosslinking agent (c) may be used alone or in combination.

  In the present invention, it is not always necessary to contain the crosslinking agent. When contained, the total content in the curable composition containing the quantum dots of the crosslinking agents (a) to (c) varies depending on the material, but is 0 to the solid content (mass) of the curable composition. 70% by weight is preferred, 0-50% by weight is more preferred, and 0-30% by weight is most preferred.

  The curable composition comprising the quantum dots of the present invention can further comprise a monomer or oligomer having one or more ethylenically unsaturated groups.

  The monomer or oligomer having one or more ethylenically unsaturated groups is preferably a compound having one or more addition-polymerizable ethylenic double bonds and a boiling point of 100 ° C. or higher under normal pressure. By containing it together with a photopolymerization initiator, which will be described later, the curable composition containing the quantum dot of the present invention can be constituted in a negative type, and from the viewpoint of further improving the curability, a positive type quantum dot You may contain in the curable composition containing this.

  Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (meta ) Acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) ) Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Polyfunctional alcohols such as nurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japan Urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, Japan Adhesion Association magazine Vol. 20, no. No. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The curable composition containing the quantum dot of this invention can further contain a photoinitiator.

  The photopolymerization initiator is contained together with the monomer or the like when the dye-containing curable composition of the present invention is configured as a negative type, and is included as necessary when configured as a positive type. The photopolymerization initiator is not particularly limited as long as it can polymerize the monomer or oligomer, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include one or more active halogen compounds selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, and benzophenone compounds. Acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like.

  Examples of the active halogen compounds that are halomethyl oxadiazo compounds include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in Japanese Patent Publication No. 57-6096, 2-trichloro, and the like. Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Methoxystyryl) -1,3,4-oxadiazole and the like.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl halomethyl-s-triazine compounds described in Japanese Patent Publication No. 59-1281, and Japanese Patent Application Laid-Open No. 53-133428. And 2- (naphth-1-yl) -4,6-bishalomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-dihalomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino 6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6-bis -Trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4 6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl)- Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s- Triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (6-methoxynaphtho- 2-yl)- , 6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphtho- 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4, 5-Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN , N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- (p-N-chloroethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2 6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N -Chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2, -Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 [O-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di ( Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2, 6 -Di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m -Fluoro-pN-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro- p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethyl) Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminopheny) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine and the like.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical Co., Ltd., manufactured by PANCHIM T series (for example, T-OMS, T-BMP, TR, T-B), Irgacure series manufactured by Ciba Geigy (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocuride (eg, Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione 2-benzyl-2-di Methylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazolyl dimer, 2- (p-dimethoxy Phenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl Dimers, benzoin isopropyl ether, and the like are also usefully used.

  These photopolymerization initiators can be used in combination with an increase / decrease agent or a light stabilizer.

  Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p -(Dimethylamino) phenyl-p- Tyrstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, etc., and tinuvin 1130 , Tinuvin 400 and the like.

  In addition to the photopolymerization initiator described above, other known initiators can be used for the curable composition containing the quantum dots of the present invention.

  Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2,367,670 are disclosed. Disclosed α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Substituted aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367 Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 Product / trihalomethyl-s-triazine compound and the like.

  The photopolymerization initiator is preferably 0.01 to 50% by weight, more preferably 1 to 30% by weight, and more preferably 1 to 20% by weight based on the total weight of the solid content in the curable composition containing the quantum dots of the present invention. Weight percent is particularly preferred. When the photopolymerization initiator is less than the above range, the polymerization is difficult to proceed. When the photopolymerization initiator exceeds the above range, the polymerization rate increases, but the molecular weight decreases, and the film strength may decrease.

  The curable composition containing the quantum dots of the present invention can further contain a thermal polymerization inhibitor. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2, 2 ' -Methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.

  The curable composition containing the quantum dot of the present invention can further contain a naphthoquinonediazide compound when the curable composition containing the quantum dot is composed of a positive type. Examples of the naphthoquinone diazide compound include o-naphthoquinone diazide-5-sulfonic acid ester or sulfonic acid amide, o-naphthoquinone diazide-4-sulfonic acid ester, or sulfonic acid amide. These esters or amides can be produced by a known method using, for example, a phenol compound described as Chemical Formula 1 in Japanese Patent Application Laid-Open No. 2-84650 and Japanese Patent Application Laid-Open No. 3-49437.

  The alkali-soluble phenol resin and the crosslinking agent are usually dissolved in a solvent at a ratio of about 2 to 50% by weight and 2 to 30% by weight, respectively, with respect to the total mass. The naphthoquinonediazide compound and the dye are usually added at a ratio of about 2 to 30% by weight and 2 to 50% by weight, respectively, with respect to the solution containing the alkali-soluble resin and the crosslinking agent. Moreover, various additives currently used in the said technical field like the smoothing agent for providing uniform applicability | paintability etc. can also be further added to the resist composition for color filters, for example.

  The curable composition containing the quantum dots of the present invention may contain a solvent, and the solvent is not particularly limited, and is selected in particular in consideration of the solubility, applicability, and safety of the quantum dots and the binder. Is preferred.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .; methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. Alkyl esters of 3-oxypropionic acid such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc .; methyl 2-oxypropionate, 2-oxo 2-oxypropionic acid alkyl esters such as ethyl propionate and propyl 2-oxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid Ethyl etc .; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ether Lenglycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferable.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

  The curable composition containing the quantum dots of the present invention includes various additives such as fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like. Further can be included.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Surfactants such as cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4) -Epoxycyclohexyl) ethyltrimeth Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  Further, when promoting the alkali solubility of the non-image area and further improving the developability of the dye-containing curable composition according to the present invention, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Addition of a low molecular weight organic carboxylic acid can be performed.

  Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  The present invention provides a color filter manufactured with a curable composition containing the quantum dots.

  When the color filter of the present invention is applied to an image display device, it emits light by the light of the display device light source, so that it can realize excellent light efficiency. Further, since light having a hue is emitted, the color reproducibility is excellent, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

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

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

  The pattern layer is a layer containing a curable composition containing the quantum dots of the present invention, and is formed by applying the curable composition containing the quantum dots, exposing, developing and heat-curing in a predetermined pattern. Can be layers.

  The pattern layer formed of the curable composition containing quantum dots includes 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. Can be provided. Upon irradiation with light, 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 is not particularly limited when applied to the image display device, but a light source that emits blue light can be used from the aspect of excellent color reproducibility.

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

  In the case where only two types of hue pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hue 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 can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is to show blue.

  The color filter including the substrate and the pattern layer may further include a barrier rib formed between the patterns and may further include a black matrix. In addition, a protective film formed on the pattern layer of the color filter may be further included.

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

  The color filter of the present invention can be applied not only to a normal liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

  The image display device of the present invention can 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 such a case, the light emitted from the light source is not particularly limited when applied to the image display device. However, from the aspect of excellent color reproducibility, a light source that emits blue light can be preferably used.

  According to another exemplary embodiment of the present invention, the image display apparatus of the present invention may include a color filter including only a pattern layer having two hues among a red pattern layer, a green pattern layer, and a blue pattern layer. Good. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles.

  In the case where only two types of hue pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hue 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 can be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is to show blue.

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

  The following examples are presented to assist in understanding the present invention, but these examples are merely illustrative of the invention and are not intended to limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the embodiments can be made within the scope of the technical idea, and such variations and modifications should be included in the appended claims. is there.

Production Example 1 Synthesis of CdSe (core) / ZnS (shell) structure photoluminescent green quantum dot particles A CdO (0.4 mmol), zinc acetate (4 mmol), oleic acid (5.5 mL) 1-Octadecene (1-Octadecene) (20 mL) was placed in a reactor and heated to 150 ° C. for reaction. Thereafter, the reaction was left under a vacuum of 100 mTorr for 20 minutes in order to remove acetic acid generated by replacing oleic acid with zinc. Then, after heating at 310 ° C. to obtain a transparent mixture, this was maintained at 310 ° C. for 20 minutes, and then 0.4 mmol of Se powder and 2.3 mmol of S powder were added to 3 mL of trioctylphosphine. The Se and S solution dissolved in was rapidly injected into the reactor containing the Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C. for 5 minutes, and then the growth was interrupted using an ice bath. Then, the quantum dots are separated using ethanol, precipitated with ethanol, and the excess impurities are washed with chloroform and ethanol to stabilize the core particles stabilized with oleic acid. Quantum dot particles A having a CdSe (core) / ZnS (shell) structure in which particles having a sum of diameter and shell thickness of 3 to 5 nm were distributed were obtained.

Production Example 2-1. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-1), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 100 ° C., 68.8 g of methacrylic acid, 36.4 g of cyclohexyl methacrylate and 136 g of propylene glycol monomethyl ether acetate were added, and a solution added with 3.2 g of t-butylperoxy-2-ethylhexyl carbonate was dropped. The mixture was added dropwise from the funnel to the flask over 2 hours, and further stirred at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 71 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110 ° C. for 6 hours, Resin D-1 having an acid value of 100 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 17000, and the molecular weight distribution (Mw / Mn) was 2.2. It was 120 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-2. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-2), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. After raising the temperature to 100 ° C., 68.8 g of methacrylic acid, 44.0 g of monomethacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd. FA-513M) and 136 g of propylene glycol monomethyl ether acetate were added. A solution to which 3.2 g of butylperoxy-2-ethylhexyl carbonate was added was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 71 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were put into the flask, and the reaction was continued at 110 ° C. for 6 hours, Resin D-2 having an acid value of 110 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 15300, and the molecular weight distribution (Mw / Mn) was 2.3. It was 130 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-3. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-3), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 100 ° C., 47.3 g of methacrylic acid, 99.9 g of 1-acryloyloxy-3-hydroxyadamantane (Aldrich) and 300 g of propylene glycol monomethyl ether acetate were added, and t-butylperoxy- A solution to which 3.2 g of 2-ethylhexyl carbonate was added was dropped into the flask over 2 hours from the dropping funnel, and further stirred at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, 35.5 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. Resin D-3 having an acid value of solid content of 95 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 18300, and the molecular weight distribution (Mw / Mn) was 2.3. It was 160 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-4. 250 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-4), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 100 ° C., 25.8 g of methacrylic acid, 50.4 g of 1-acryloyloxy-3-hydroxyadamantane (Aldrich), 56.7 g of acrylophenone and 110 g of propylene glycol monomethyl ether acetate are added. A solution having 3.6 g of azobisisobutyronitrile added dropwise to the flask over 2 hours from a dropping funnel and further stirred at 100 ° C. for 5 hours, and a solid content acid value of 115 mgKOH / g D-4 was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 19000, and the molecular weight distribution (Mw / Mn) was 2.3. It was 160 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-5. 250g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-5), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 100 ° C., 25.8 g of methacrylic acid, 14.4 acryloyloxy-3-hydroxyadamantane (Aldrich) 44.4 g, 44.8 g acrylophenone, 10.0 g methyl methacrylic acid and propylene A solution in which 110 g of glycol monomethyl ether acetate was added, and 3.6 g of azobisisobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and further stirred at 100 ° C. for 5 hours. Resin D-5 having a weight of 115 mgKOH / g was obtained. The weight average molecular weight in terms of polystyrene measured by GPC was 19000, and the molecular weight distribution (Mw / Mn) was 2.2. It was 135 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-6. 250 g of propylene glycol monomethyl ether acetate was put into a flask equipped with a synthetic stirrer of alkali-soluble resin (D-6), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask was filled with nitrogen from air. After raising the temperature to 100 ° C., 25.8 g of methacrylic acid, 18.8 g of 2-norbornene, 44.8 g of acrylophenone, 10.0 g of methyl methacrylic acid and 110 g of propylene glycol monomethyl ether acetate were added, and azobisiso A solution to which 3.6 g of butyronitrile was added was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 5 hours to obtain a resin D-6 having a solid acid value of 105 mgKOH / g. It was. The polystyrene equivalent weight average molecular weight measured by GPC was 16,300, and the molecular weight distribution (Mw / Mn) was 2.4. It was 150 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-7. 180 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-7), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 80 ° C., 20.0 g of methyl methacrylic acid, 55.2 g of n-butyl acrylate, 30 g of glycidyl methacrylate and 71 g of propylene glycol monomethyl ether acetate were added, and t-butyl peroxy-2-ethylhexyl carbonate was added. The solution to which 2 g was added was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 36.0 g of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and reacted at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 4.5 parts of succinic anhydride was added, and the mixture was reacted at 80 ° C. for 6 hours to obtain Resin D-7 having an acid value of 80 mg KOH / g as a solid content. . The weight average molecular weight in terms of polystyrene measured by GPC was 15200, and the molecular weight distribution (Mw / Mn) was 2.1. It was -1.3 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-8. 180 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-8), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 80 ° C., 20.0 g of methyl methacrylic acid, 55.2 g of 2-ethylhexyl acrylate, 30 g of glycidyl methacrylate and 71 g of propylene glycol monomethyl ether acetate were added, and t-butylperoxy-2-ethylhexyl carbonate was added. The solution to which 2 g was added was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 36.0 g of methacrylic acid, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and reacted at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 4.5 parts of succinic anhydride was added, and the mixture was reacted at 80 ° C. for 6 hours to obtain Resin D-8 having a solid content acid value of 45 mgKOH / g. . The weight average molecular weight in terms of polystyrene measured by GPC was 7500, and the molecular weight distribution (Mw / Mn) was 2.1. It was -19.3 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-9. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-9), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. After raising the temperature to 100 ° C., 105.7 g of benzyl methacrylate, 17.2 g of methacrylic acid, 26.0 g of 2-hydroxyethyl methacrylic acid, and 136 g of propylene glycol monomethyl ether acetate were added, and azobisisobutyronitrile 3. The solution to which 6 g was added was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 100 ° C. for 3 hours to obtain Resin D-9 having a solid acid value of 60 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 18000, and the molecular weight distribution (Mw / Mn) was 2.2. It was 80 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-10. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-10), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 100 ° C., 105.7 g of benzyl methacrylate, 34.4 g of methacrylic acid and 136 g of propylene glycol monomethyl ether acetate were added, and a solution containing 3.6 g of azobisisobutyronitrile was added from the dropping funnel. The mixture was dropped into the flask over time, and further stirred at 100 ° C. for 3 hours to obtain Resin D-10 having an acid value of solid content of 130 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 17000, and the molecular weight distribution (Mw / Mn) was 2.2. It was 100 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-11. 182 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-11), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. After heating to 100 ° C., 76.8 g of n-butyl methacrylate, 17.2 g of methacrylic acid, 26.0 g of 2-hydroxyethyl methacrylic acid and 136 g of propylene glycol monomethyl ether acetate were added, and azobisisobutyronitrile was added. The solution to which 3.6 g was added was dropped from the dropping funnel into the flask over 2 hours, and further stirred at 100 ° C. for 3 hours to obtain Resin D-11 having a solid content acid value of 62 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 15500, and the molecular weight distribution (Mw / Mn) was 2.2. It was -20 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Production Example 2-12. 100 g of propylene glycol monomethyl ether acetate is placed in a flask equipped with a synthetic stirrer of alkali-soluble resin (D-12), a reflux condenser with a thermometer, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask is filled with nitrogen from air. Then, after raising the temperature to 80 ° C., 10.2 g of 2-ethylhexyl acrylate, 0.7 g of 4-methylstyrene, 76 g of glycidyl methacrylate, 3 g of n-dodecyl mercapto and 100 g of propylene glycol monomethyl ether were added, and azobisisobutyro The solution to which 5 g of nitrile was added was dropped into the flask over 2 hours from the dropping funnel, and stirring was further continued at 80 ° C. for 4 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 10.4 g of acrylic acid were put into the flask, and reacted at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution is lowered to room temperature, 2.7 g of succinic anhydride is added, and the reaction is performed at 80 ° C. for 6 hours to obtain a resin D-12 having an acid value of 16.45 mgKOH / g as a solid content. It was. The polystyrene equivalent weight average molecular weight measured by GPC was 5450, and the molecular weight distribution (Mw / Mn) was 2.1. It was -28.4 degreeC as a result of measuring glass transition temperature with a differential scanning calorimeter.

Examples 1-8 and Comparative Examples 1-4: Manufacture of a self-luminous photosensitive resin composition As described in Table 1 and Table 2 below, after mixing the components, the total solid content was 20% by weight. Then, after diluting with propylene glycol monomethyl ether acetate, the mixture was sufficiently stirred to obtain a self-luminous photosensitive resin composition.

Production Example of Color Filter (Glass Substrate) A color filter was produced using the self-luminous photosensitive resin composition produced in Examples 1-8 and Comparative Examples 1-4. That is, each of the self-luminous photosensitive resin compositions was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. . Subsequently, a test photomask having a regular square transmission pattern of horizontal x vertical 20 mm x 20 mm and a line / space pattern of 1 μm to 100 μm is placed on the thin film, and an ultraviolet ray is irradiated at an interval of 100 μm from the test photomask. did.

At this time, the ultraviolet light source is irradiated with light at an exposure amount (365 nm) of 200 mJ / cm ² in an atmospheric atmosphere using an ultrahigh pressure mercury lamp (trade name USH-250D) manufactured by Ushio Electric Co., Ltd. No special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development. The glass plate provided with this thin film was washed with distilled water, 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 pattern manufactured as described above was 3.0 μm.

Measurement of fine pattern The pattern size obtained through the 100 μm line / space pattern mask of the color filter on which the self-luminous pixels were formed was measured through OM equipment (ECLIPSE LV100POL, manufactured by Nikon Corporation). .

  Fine pattern (Δ μm) = (line / space pattern mask size, 100 μm) − (measured pixel pattern size)

  If the value of the fine pattern is larger than 10 μm, it is difficult to implement a fine pixel, and if it has a negative value, a process failure can be caused.

Measurement of light intensity (Intensity) 365 nm Tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) on a pattern (Pattern) portion formed of a regular square pattern of 20 mm × 20 mm among the color filters in which the self-luminous pixels are formed. In Examples 1-8 and Comparative Examples 1-4, the emission intensity (Intensity) in the 550 nm region was measured using a spectrum meter (manufactured by Ocean Optics). It can be determined that the higher the measured luminescence intensity (Intensity), the more excellent self-luminous properties are exhibited, and the measurement results of the luminescence intensity (Intensity) are shown in Table 3 below. Moreover, hard bake (hard bake) is carried out at 230 ° C. for 60 minutes, the emission intensity (Intensity) before hard baking and the emission intensity (Intensity) after hard baking are measured, and the level at which the luminous efficiency is maintained is confirmed. Table 3 shows the emission intensity maintenance rate.

  As shown in Table 3, by including the binders used in Examples 1 to 8 presented in the present invention, the emission intensity and emission intensity maintenance ratio are increased, and a fine pattern can be produced. An excellent photosensitive resin composition capable of producing a high-resolution color filter can be obtained.

  Referring to Comparative Examples 1 to 3 and Examples 1 to 8, when using a binder having a double bond at the end, a crosslinking ability, and compatibility with the quantum dot and the ligand on the surface of the quantum dot, By acting as a protecting group on the surface of the quantum dot, it is possible to confirm the effect of having excellent emission intensity and a small extinction width during the process. Further, referring to Comparative Example 4 and Examples 7 to 8, even if the emission intensity is high, if the glass transition temperature (Tg) is −20 ° C. or less, it is impossible to form a high-resolution fine pattern. It can be confirmed that it is impossible.

Claims (7)

Including a binder and quantum dots,
The binder includes one or more of the following chemical formula 1, chemical formula 2, and combinations thereof, and a curable composition containing quantum dots:
[Chemical Formula 1]

(In Formula 1 above,
R ₁ represents hydrogen or a C1-C6 alkyl group,
R ₂ represents oxygen, —NH— or

Group,
R ₃ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group,
R ₄ represents a group containing an unsaturated double bond. )
[Chemical formula 2]

(In Formula 2 above,
R _{5 to} R ₆ are each independently the same or different and each represents hydrogen or a C1-C6 alkyl group;
R ₇ is oxygen, —NH— or

Group,
R ₈ represents a C1-C30 alkylene group, a C1-C30 alkyleneoxy group, or a C1-C30 ethyloxycarbonylaminoethyl group,
R ₉ represents a group containing an unsaturated double bond,
X represents a value of 0 <X <100. ) The binder is
The curable composition containing quantum dots according to claim 1, wherein the glass transition temperature is -20 to 250 ° C. Of the curable composition containing the quantum dots, with respect to the total weight part of solids,
10 to 90 wt% of the binder and 3 to 80 wt% of the quantum dots,
The curable composition containing quantum dots according to claim 1 or 2, wherein the remainder contains a photopolymerization compound and a photopolymerization initiator. The quantum dots are
It is a red quantum dot, a green quantum dot, or a blue quantum dot, The curable composition containing the quantum dot in any one of Claims 1-3 characterized by the above-mentioned.   The quantum dot has a core selected from the group consisting of CdSe, CdS, ZnS, ZnSe, ZnTe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and ZnO. And wherein the shell comprises one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe. The curable composition containing the quantum dot in any one of claim | item 1-4.   A color filter manufactured with a curable composition comprising the quantum dots according to claim 1.   An image display device comprising the color filter according to claim 6.