JP2019532348A - Quantum dot dispersion, self-luminous photosensitive resin composition containing the same, color filter manufactured using the same, and image display device - Google Patents

Abstract

The quantum dot dispersion according to the present invention includes: a quantum dot; and a first solvent having a dielectric constant of less than 12.0 at 20 ° C., provided that the halogenated hydrocarbon solvent; the aromatic hydrocarbon solvent; and the aliphatic It is characterized by not containing a saturated hydrocarbon solvent.

Description

  The present invention relates to a quantum dot dispersion containing a solvent having a specific dielectric constant, a self-luminous photosensitive resin composition containing the same, a color filter produced using the same, and an image display device.

  A color filter is a thin-film optical component that extracts three colors of red, green, and blue from white light and enables them in fine pixel units. Each pixel has a size of several tens to several hundreds of micrometers. Degree. Such a color filter has a plurality of colors (in order to form a black matrix layer formed in a pattern defined on a transparent substrate and each pixel in order to shield a boundary portion between each pixel. Usually, a pixel portion in which the three primary colors of red R, green G, and blue B) are arranged in a predetermined order is sequentially stacked.

  Recently, a pigment dispersion method using a pigment-dispersed photosensitive resin has been applied as one of the methods for embodying a color filter, but the light emitted from the light source passes through the color filter in the process. A part of the color filter is absorbed by the color filter, resulting in a decrease in light efficiency and a problem that color reproduction is deteriorated due to the characteristics of the pigment contained in the color filter.

  In particular, as color filters are used in various fields including various image display devices, not only excellent pattern characteristics, but also high color reproducibility and performance such as high brightness and high contrast ratio. However, in order to solve such a problem, a method for producing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.

  Quantum dots contained in the self-luminous photosensitive resin composition are generally purchased and used in a commercially available form, and such quantum dots are composed of chloroform, toluene, n-hexane, or benzene. Dispersed in non-polar solvents that are harmful to the human body. In the case of the above-mentioned solvent, it is a highly volatile compound (Volatile Organic Compound), or is carcinogenic, neurotoxic, and has a high risk of abnormal reproductive functions. is required.

  Korean Patent Publication No. 2015-0034013 relates to a quantum dot-resin nanocomposite and a method for producing the same, and relates to a quantum dot-resin nanocomposite in which a curable resin and a large number of quantum dots exist in the form of nanoparticles. Related contents are disclosed.

Korean Patent Publication No. 2006-0069393 relates to a method of manufacturing a light conversion composite material, a light conversion composite material, a light conversion film including the light conversion composite material, a backlight unit, and a display device, and a matrix resin; and a quantum dispersed in the matrix resin It is a light conversion composite material including dot-polymer beads, and the light conversion composite material is a scattering intensity (intensity) graph by wave number measured by small angle X-ray scattering (Small Angle X-ray Scattering). The content regarding the light conversion composite material whose wavenumber q of a peak point (peak point) is 0.0056? ^{-1 to} 0.045? ^-1 is disclosed.

  In the case of the above-mentioned document, a solvent harmful to the human body is used as a solvent, or since the dispersion characteristics are not excellent, there is a problem in that it cannot be applied to a color filter because it is not patterned.

  Therefore, development of quantum dot dispersions and self-luminous photosensitive resin compositions that are excellent in dispersibility and capable of realizing excellent light emission characteristics despite containing no harmful components to the human body is required.

Korean Patent Publication No. 2015-0034013 (2015.04.02) Korean Patent Publication No. 2006-0069393 (2016.06.16.)

  The present invention provides a quantum dot dispersion that does not contain a solvent harmful to the human body, and a self-luminous photosensitive resin composition containing the quantum dot dispersion.

  In addition, the present invention provides a quantum dot dispersion excellent in dispersibility and light emission characteristics, and a self-luminous photosensitive resin composition containing the quantum dot dispersion.

  In addition, the present invention provides a color filter and an image display device that are manufactured using the above-described quantum dot dispersion and self-luminous photosensitive resin composition and have excellent light emission characteristics.

  In order to achieve the above object, a quantum dot dispersion according to the present invention includes: a quantum dot; and a first solvent having a dielectric constant of less than 12.0 at 20 ° C., provided that the halogenated hydrocarbon solvent; A hydrogen-based solvent; and an aliphatic saturated hydrocarbon-based solvent.

  In addition, the present invention provides a self-luminous photosensitive resin composition further comprising at least one selected from the group consisting of the above-described quantum dot dispersion; and a photopolymerizable compound; an alkali-soluble resin; a photopolymerization initiator; and a second solvent. Offer things.

  Moreover, this invention provides the color filter containing the hardened | cured material of the self-light-emitting photosensitive resin composition mentioned above.

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

  The quantum dot dispersion according to the present invention and the self-light-emitting photosensitive resin composition including the quantum dot dispersion have an advantage of being excellent in dispersibility and being capable of realizing excellent light-emitting characteristics because they contain a solvent having a specific dielectric constant. There is an advantage that it does not contain a human toxic substance.

  Moreover, the color filter and image display apparatus manufactured with the self-light-emitting photosensitive resin composition according to the present invention have an advantage of excellent light emission characteristics.

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

  In the present invention, when an arbitrary member is located "on" another member, this is not only when the arbitrary member is in contact with the other member, but also between the two members. Including the case where exists.

  In the present invention, when any part “comprises” a certain component, this does not exclude other components and can further include other components unless otherwise stated. Means.

<Quantum dot dispersion>
One aspect of the present invention relates to a quantum dot dispersion. Specifically, one aspect of the present invention includes: a quantum dot; and a first solvent having a dielectric constant less than 12.0 at 20 ° C., wherein a halogenated hydrocarbon solvent; an aromatic hydrocarbon solvent; The present invention relates to a quantum dot dispersion containing no aliphatic saturated hydrocarbon solvent.

  The quantum dot dispersion according to the present invention includes quantum dots. The quantum dot may refer to a nano-sized semiconductor material. Atoms form molecules, and molecules form an assembly of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots. When the quantum dot is excited by receiving energy from the outside, the quantum dot emits energy by an energy band gap corresponding to the quantum dot.

  The color filter manufactured with the self-light-emitting photosensitive resin composition according to the present invention can emit light (photoluminescence) by light irradiation by including the quantum dots.

  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 self-light-emitting photosensitive resin composition according to the present invention is included, the color filter itself emits light by the light of the light source, so that more excellent light efficiency can be realized, Since light having a color is emitted, the color reproducibility is further improved, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

  Any quantum dot particle that can emit light upon stimulation with light is not particularly limited. For example, selected from the group consisting of Group II-VI semiconductor compounds; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; Group IV elements or compounds containing these; and combinations thereof, which may be used alone or in combination They can be used in combination.

  Specifically, 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, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnSe, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and a mixture of these. Selected from the group consisting of CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof. Although it selected from the group consisting of classical element compound, but is not limited thereto.

  The group III-V semiconductor compound is a two-element compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; GANP, GANAS, A ternary compound selected from the group consisting of GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and Selected from the group consisting of classical element compound selected from the group consisting of a mixture of these.

  The IV-VI group semiconductor compound may be a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe and mixtures thereof; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbS, SnPbS, Three or more elemental compounds selected from the group consisting of SnPbTe and mixtures thereof; and one or more selected from the group consisting of four elemental compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe and mixtures thereof, It is not limited to these.

  Although not limited thereto, the group IV element or the compound containing the element is an elemental compound selected from the group consisting of Si, Ge and a mixture thereof; and a two-element compound selected from the group consisting of SiC, SiGe and a mixture thereof Selected from the group consisting of

  The quantum dots may have a homogenous single structure; a double structure such as a core-shell, a gradient structure, or the like; or a mixed structure thereof.

  Specifically, in the core-shell dual structure, the materials constituting the core and the shell may be composed of the above-mentioned different semiconductor compounds. For example, the core may include at least one material selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. Absent. The shell may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

  The quantum dot may be one in which a part of the surface is substituted with an organic ligand, but is not limited thereto. The organic ligand is preferable because it can be bonded to the surface of the quantum dot to stabilize the quantum dot. The organic ligands include, but are not limited to, C5-C20 alkyl carboxylic acid, alkenyl carboxylic acid or alkynyl carboxylic acid; pyridine; mercapto alcohol; thiol; phosphine ( phosphine oxide; primary amine; secondary amine; and the like.

  In the present invention, a method of replacing a part of the surface of the quantum dot with an organic ligand is not limited, and a normal method performed in the art can be used.

  The quantum dots may be synthesized by a wet chemical process, a metalorganic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy process (MBE). It is not something.

  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 control the growth of the crystal, so that the metal organic chemical vapor deposition process and molecular beam epitaxy Since the growth of nanoparticles can be controlled using a process that is easier and less expensive than the vapor deposition method, it is preferable to manufacture the quantum dots according to the present invention using the wet chemical process.

  The quantum dots may be included in an amount of 20 to 99 parts by weight, preferably 30 to 99 parts by weight, more preferably 50 to 99 parts by weight, based on 100 parts by weight of the total solid content of the quantum dot dispersion. When the quantum dots are included in the range, it is possible to provide a self-luminous photosensitive resin composition having excellent photosensitive characteristics. When the quantum dots are included below the range, the photosensitive characteristics may be slightly deteriorated. When the quantum dots are included beyond the range, other configurations described later than the quantum dots, for example, alkali-soluble resins, photopolymerizability, etc. Since the content of the composition such as the compound is relatively small, there is a problem that the production of the color filter may be somewhat difficult, and therefore it is preferably included in the above range.

  The quantum dot dispersion according to the present invention includes a first solvent having a dielectric constant of less than 12.0 at 20 ° C. However, the solvent according to the present invention does not include a halogenated hydrocarbon solvent; an aromatic hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent.

  Examples of the halogenated hydrocarbon solvent include, but are not limited to, chloroform, dichloromethane, methylene chloride carbon tetrachloride, dichloroethane, tetrachloroethane, and the like.

  The aromatic hydrocarbon solvent may include benzene, toluene, dichlorobenzene, xylene and the like, but is not limited thereto.

  The aliphatic saturated hydrocarbon solvent may include, but is not limited to, a chain alkane such as N-hexane, pentane, and heptane, a cyclic alkane such as cyclopentane and cyclohesisan, and kerosene.

  Specifically, the first solvent according to the present invention is a halogenated hydrocarbon solvent such as chloroform or dichloromethane; an aromatic hydrocarbon solvent such as benzene or toluene; or an aliphatic saturated hydrocarbon such as N-hexane. The content of the system solvent may be 100 ppm, specifically 50 ppm, more specifically 10 ppm or less.

  Since the solvent according to the present invention does not contain a solvent harmful to the human body, there is an advantage that the worker can be protected from a potential danger.

  In still another embodiment of the present invention, the first solvent may have a dielectric constant of less than 8.0 at 20 ° C.

  In still another embodiment of the present invention, the first solvent may have a dielectric constant of less than 6.0 at 20 ° C.

  The quantum dot dispersion according to the present invention has an advantage of excellent quantum dot dispersion characteristics by including the first solvent satisfying the dielectric constant value. Accordingly, the color filter and the image display device manufactured with the self-light-emitting photosensitive resin composition containing the quantum dot dispersion according to the present invention have an advantage that the light emission characteristics are excellent.

  When the dielectric constant of the first solvent is 12.0 or higher at 20 ° C., the dispersibility of the quantum dots is somewhat reduced, and this causes a phenomenon that the quantum dots are aggregated, resulting in a decrease in overall light emission characteristics. In addition, it is preferable to use a first solvent having a dielectric constant of less than 12.0 at 20 ° C. because a color filter with non-uniform performance can be manufactured.

  In still another embodiment of the present invention, the first solvent is methyl isoamyl ketone, diisobutyl ketone, diethyl carbonate, butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl isobutyrate, 2-ethylhexyl acetate, hexyl acetate, neryl acetate. , Dipropylene glycol dimethyl ether and dipropylene glycol methyl ether acetate, ethyl o-formate, ethyl butyrate, diethyl acetal, methyl hexanoate, methyl octanoate, ethyl isovalerate, methyl 3-methylbutanoate, isopentyl 3 -Methylbutanoate, isopentylbutanoate, ethyl methyl carbonate, pentylpentanoate, isoamylpropionate, isobutyl Ruisovalerate, propyl isovalerate, 2- (2- (vinyloxy) ethoxy) propane, 1-allyloxy-2-isopropoxy-ethane, (2-isobutoxy-ethoxy) -ethene, 1-vinyloxy-2-isopentoxy-ethane, One or more selected from the group consisting of 1-vinyloxy-2-pentoxy-ethane may be included.

  The first solvent may be included in an amount of 25 to 95 parts by weight, preferably 30 to 95 parts by weight, and more preferably 40 to 90 parts by weight with respect to 100 parts by weight of the entire quantum dot dispersion. When the first solvent is included in the range with respect to 100 parts by weight of the entire quantum dot dispersion, it is preferable because dispersibility of the quantum dots can be improved. When the first solvent is included below the range, the optical characteristics are advantageous, but the dispersion characteristics may be somewhat deteriorated. When the first solvent is exceeded, the dispersion characteristics are advantageous, but the optical characteristics are slightly decreased. Therefore, it is preferable to satisfy the above range.

  In still another embodiment of the present invention, the quantum dot dispersion may further include one or more selected from the group consisting of a phosphate ester dispersant, an acrylic dispersant, and a urethane dispersant.

  When the quantum dot dispersion further includes one or more selected from the group consisting of the phosphate ester dispersant, the acrylic dispersant, and the urethane dispersant, the dispersibility between the quantum dots and the first solvent is improved. Thus, there is an advantage of excellent quantum efficiency.

The phosphate ester dispersant may include a phosphate ester compound, and the phosphate ester compound may be phosphate ester ((HO) ₂ PO (OR)) or phosphoric acid (H _3). It is possible to include a hydroxy group present in PO ₄ ) or a hydrogen atom of the hydroxy group substituted or unsubstituted with another functional group. For example, the phosphate ester compound may be expressed in the form of (H ₂ PO ₃ ⁻ ), but is not limited thereto. In the present invention, the “phosphate ester type” may also include one or more selected from the group consisting of phosphorous acid derivatives, phosphoric acid derivatives, phosphonic acid derivatives, and phosphinic acid derivatives.

  When the dispersant contains the phosphate ester compound, there is an advantage that a decrease in light efficiency and a poor photosensitive property can be suppressed.

  The phosphate ester compound may further include one or more of a polyether portion, a polyester portion, and a phosphate group in one molecule.

  In the present invention, “poly-” can refer to a compound composed of a large number of repeating units, and the “polyether part” and “polyester part” are each a repeating unit containing an ether group or an ester group. Can refer to a portion consisting of 1-20. Preferably, in the present invention, the repeating unit may consist of 5 to 20, more preferably 10 to 20, and in this case, there is an advantage that the compatibility is excellent.

  When the phosphate ester compound further includes a polyether moiety in one molecule, there is an advantage that compatibility with an alkali-soluble resin described later is improved, and the phosphate ester compound has a polyester moiety in one molecule. When it contains further, there exists an advantage which the compatibility with alkali-soluble resin and the solubility characteristic with respect to an alkali developing solution improve. When the phosphoric acid ester-based compound further contains a phosphate group in one molecule, it can serve as a protective layer through adsorption on the surface of the quantum dot, and has an advantage of deaggregating the quantum dot.

  Preferably, the phosphoric acid ester-based compound according to the present invention can include a polyether part, a polyester part and a phosphoric acid group in one molecule. In this case, the quantum dots are disaggregated to reduce the dispersed particle size, Since it has compatibility with an alkali-soluble resin and solubility in an alkali developer, it is most preferable because it has the advantage of being advantageous for pattern formation.

  In the present invention, the “acid value” is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is a self-luminous photosensitive resin composition described later. Can be involved in the solubility. When the acid value of the phosphoric ester compound is 10 (KOHmg / g) or more, specifically 10 to 200 (KOHmg / g), from the viewpoint of the development rate of the self-light-emitting photosensitive resin composition containing the dispersant. preferable. If the acid value is less than the above range, it may be difficult to ensure a sufficient development speed.If the acid value exceeds the above range, the adhesion with the substrate is reduced and pattern short circuit is likely to occur. Since the storage stability of a typical composition may decrease and the viscosity may increase, it is preferable to satisfy the above range.

  Examples of the acrylic dispersant include an acrylic block copolymer. As the acrylic block copolymer, a block copolymer having a block containing a basic group and an acid group and a block containing no basic group or acid group is preferable.

  The basic group and the acid group (hereinafter, these groups may be collectively referred to as “quantum dot adsorption group”) each have an action of adsorbing the above-described quantum dots.

  As a quantum dot adsorption block containing the said quantum dot adsorption group, what is comprised by utilizing the monomer which has an acid group with the monomer which has a basic group is mentioned.

  Examples of the monomer having a basic group include monomers having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group. Specific examples of the monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, diethylacrylamide, dimethylaminopropylmethacrylamide, and acryloylmorpholine. , Vinylimidazole, 2-vinylpyridine, monomer having an amino group and a caprolactone skeleton; a reaction product of a compound having a glycidyl group such as glycidyl (meth) acrylate and a compound having one secondary amino group in the molecule ; (Meth) acryloylalkyl isocyanate compound and 4- (2-aminomethyl) -pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-hydroxyethyl) pyridine, 1- (2-aminoethyl)- Piperazine, 2-amino-6-methoxy Nzochiazoru, 1- (2-hydroxyethyl-imidazole), N, N- diallyl melamine, N, such as the reaction product of N- dimethyl-1,3-propane diamine.

  Examples of the monomer having an acid group include monomers having a carboxy group and a sulfo group. Examples of the monomer having a carboxy group include unsaturated monocarboxylic acid compounds such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid, and itaconic acid, and half esters thereof. . Examples of the monomer having a sulfo group include 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, and styrenesulfonic acid.

  Examples of the block not containing the quantum dot adsorbing group include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl chloride; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like. Examples include blocks derived from unsaturated carboxylic acid alkyl esters; unsaturated carboxylic acid arylalkyl esters such as benzyl (meth) acrylate; polycaprolactone-containing compounds, polyalkylene glycol monoester compounds, and the like.

  The acrylic block copolymer can be obtained by a conventionally known polymerization method such as living anion polymerization.

  The amine value of the acrylic block copolymer is usually 0 to 200 mgKOH / g, preferably 0 to 120 mgKOH / g, more preferably 0 to 80 mgKOH / g.

  Commercially available products of the acrylic block copolymer include “Disperbyk (registered trademark) -112 (amine value 36 mgKOH / g)” and “Disperbyk (registered trademark) -2000 (amine value 4 mgKOH / g) manufactured by Big Chemie Japan. g) "," Disperbyk-2001 (amine number 29 mgKOH / g) "," Disperbyk (registered trademark) -2020 (amine number 38 mgKOH / g) "," Disperbyk (registered trademark) -2050 (amine number 30 mgKOH / g) " , “Disperbyk (registered trademark) -2070 (amine value 20 mg KOH / g)” and the like.

  Examples of the urethane dispersant include a compound having a number average molecular weight of 300 to 10,000 having one or more hydroxy groups in the molecule and a basic group-containing compound having a functional group capable of reacting with an isocyanate group in the molecule. A dispersant obtained by reacting with an isocyanate group of an isocyanate compound can be used.

  As a method for obtaining such a urethane-based dispersant, a method described in JP-A-60-166318 can be used.

Examples of the polyisocyanate compound include isocyanate compounds having two or more isocyanate groups,
2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5- Aromatic diisocyanate compounds such as naphthylene diisocyanate and 3,3′-dimethylbiphenyl-4,4′-diisocyanate;
Aliphatic polyisocyanates and alicyclics such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethylene) cyclohexane Formula polyisocyanate;
A polyisocyanate having an isocyanuric group derived from the diisocyanate (such as a polyisocyanate having an isocyanuric group formed by trimerization of the diisocyanate);
A polyisocyanate obtained by reacting a diisocyanate with a polyol;
And polyisocyanates obtained by burette reaction of diisocyanate compounds.

  Among the polyisocyanate compounds, polyisocyanates having an isocyanuric group derived from diisocyanates such as tolylene diisocyanate and isophorone diisocyanate are preferable.

  Examples of the compound having one or more hydroxy groups in the molecule include polyether compounds and polyester compounds.

Examples of the polyether compound include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol;
Alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol;
Examples include modified products of low-molecular monools such as methanol and ethanol.

  Examples of the modified product of the low-molecular monool include an ethylene oxide modified product, a propylene oxide modified product, a butylene oxide modified product, and a tetrahydrofuran modified product.

Examples of the polyester compound include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol. Modified products of alkylene glycols of
Modified products of low-molecular monools such as methanol and ethanol;
An esterified product of an aliphatic dicarboxylic acid such as adipic acid or dimer acid and a polyol such as neopentyl glycol or methylpentanediol; that is, an aliphatic polyester polyol;
An esterified product of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; that is, a polyester polyol (such as an aromatic polyester polyol);
Polyhydric hydroxy group compounds such as polycarbonate polyol, acrylic polyol, polytetramethylene hexaglyceryl ether (hexaglycerin modified tetrahydrofuran), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid Esterified products with dicarboxylic acids such as
And polyhydric hydroxy group-containing compounds such as monoglycerides obtained by a transesterification reaction between a polyhydric hydroxy group-containing compound such as glycerin and a fatty acid ester.

  Examples of modified products of alcohols such as alkylene glycols and low-molecular monools include ε-caprolactone modified products, γ-butyrolactone modified products, δ-valerolactone modified products, methyl valerolactone modified products, and the like.

  Among the compounds having one or more hydroxy groups in the molecule, ε-caprolactone adducts of alcohols are preferable.

  The number average molecular weight of the compound having one or more hydroxy groups in the molecule is 300 to 10,000, preferably 300 to 6,000.

  The number average molecular weight and the weight average molecular weight can be measured by column chromatography.

  The basic group-containing compound having a functional group capable of reacting with an isocyanate group in the molecule is not particularly limited, and a compound usually used in the technical field of dispersants can be used.

  As the basic group-containing compound, a compound having an active hydrogen atom of Zerebitinoff and at least one nitrogen atom-containing basic group, for example, a polyol having an N, N-disubstituted amino group or a heterocyclic nitrogen atom, At least one compound selected from the group consisting of polythiols and amines is preferred.

  Examples of such a basic group-containing compound include N, N-dimethyl-1,3-propanediamine, N, N-diethyl 1,4-butanediamine, 2-dimethylaminoethanol, and 1- (2-aminoethyl). -Piperazine, 2- (1-pyrrolidyl) -ethylamine, 4-amino-2-methoxypyrimidine, 4- (2-aminoethyl) -pyridine, 1- (2-hydroxyethyl) -piperazine, 4- (2-hydroxy Ethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, 2-amino-6-methoxybenzothiazole, N, N-diallyl-melamine, 3-amino-1,2,4-triazole, 1- (2 -Hydroxyethyl) -imidazole, 3-mercapto-1,2,4-triazole and the like. Of these, amines having a heterocyclic nitrogen atom are preferred.

  The urethane-based dispersant can be synthesized by a conventionally known method.

  The amine value of the urethane-based dispersant is preferably 0 to 200 mgKOH / g, more preferably 0 to 120 mgKOH / g, and more preferably 0 to 80 mgKOH / g. The amine value of the urethane-based dispersant is preferably 0 to 55 mgKOH / g, more preferably 5 to 40 mgKOH / g.

  Examples of commercially available urethane dispersants include Disperbyk-161 (amine value 11 mgKOH / g, manufactured by Big Chemie), Disperbyk-162 (amine value 13 mgKOH / g manufactured by Big Chemie), Disperbyk-167 (amine value 13 mgKOH / g, Big Chemie manufacture), Disperbyk-182 (amine value 13 mgKOH / g, manufactured by Big Chemie), and the like.

  In this specification, the amine value means an amine value per 1 g of the solid content of the dispersant, and a potentiometric titration method [e.g., COMMITITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK-900), manufactured by Hiranuma Sangyo Co., Ltd.] and then converted to the equivalent of potassium hydroxide.

  The dispersant may be included in an amount of 1 to 250 parts by weight, preferably 3 to 200 parts by weight, and more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the total solid content of the quantum dots. When the dispersant is included in the above range, the quantum dot is excellent in deaggregation effect, and the precipitation phenomenon due to the difference in polarity in the quantum dot dispersion according to the present invention and the self-light-emitting photosensitive resin composition including the same is suppressed. This is preferable because it can serve as a protective layer for the quantum dots during the color filter manufacturing process.

<Self-luminous photosensitive resin composition>
Still another aspect of the present invention is a self-luminous photosensitizer further comprising at least one selected from the group consisting of the above-described quantum dot dispersion; and a photopolymerizable compound; an alkali-soluble resin; a photopolymerization initiator; and a second solvent. The present invention relates to a functional resin composition.

  In still another embodiment of the present invention, the quantum dot dispersion is 3 to 80 parts by weight, preferably 5 to 70 parts by weight, more preferably 100 parts by weight of the self-luminous photosensitive resin composition. It may be contained in 10 to 60 parts by weight. When the self-luminous photosensitive resin composition according to the present invention contains the above-described quantum dot dispersion within the above range, there is an advantage that it is possible to produce a color filter having excellent light emission characteristics. When the quantum dot dispersion is included below the range, the light emission characteristics may be slightly deteriorated. When the quantum dot dispersion is included beyond the range, the content of other components is relatively decreased. The formation of the pattern may be somewhat difficult and the reliability may be lowered, so that it is preferably included in the above range.

  The self-luminous photosensitive resin composition according to the present invention may contain a photopolymerizable compound. The photopolymerizable compound contained in the light-emitting photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and includes a monofunctional monomer, a bifunctional monomer, Other polyfunctional monomers are exemplified.

  The kind of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. Is mentioned.

  The type of the bifunctional monomer is not particularly limited. For example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like.

  The kind of the polyfunctional monomer is not particularly limited. For example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Examples include hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Of these, polyfunctional monomers having two or more functions are preferably used.

  Examples of the commercially available photopolymerizable compound include A95550 from Shin-Nakamura Co., but are not limited thereto.

  The photopolymerizable compound is 5 to 50 parts by weight, specifically 15 to 45 parts by weight, more specifically 20 to 37 parts by weight with respect to 100 parts by weight as a whole of the solid content of the light-emitting photosensitive resin composition. Can be included. When the photopolymerizable compound is included in the above range, there is an advantage that it is preferable from the viewpoint of the strength and smoothness of the pixel portion.

  When the photopolymerizable compound is included in less than the range, the strength of the pixel portion may be slightly reduced, and when the photopolymerizable compound is included in excess of the range, the smoothness may be slightly decreased. It is preferable to be included in the range.

  The self-luminous photosensitive resin composition according to the present invention can contain an alkali-soluble resin.

  The alkali-soluble resin can make the non-exposed portion of the color filter manufactured by the self-light-emitting photosensitive resin composition be alkali-soluble and removable, and can leave the exposed area. In addition, when the self-luminous photosensitive resin composition includes the alkali-soluble resin, the quantum dots can be uniformly dispersed in the composition, and the brightness is maintained by protecting the quantum dots during the process. Can play a role.

  The said alkali-soluble resin by this invention can select and use what has an acid value of 50-200 (KOHmg / g). In addition, the alkali-soluble resin can take into consideration limitations on molecular weight and molecular weight distribution (Mw / Mn) in order to improve surface hardness for use in a color filter. The weight average molecular weight is preferably 3,000 to 35,000, preferably 5,000 to 32,000, and the molecular weight distribution is 1.5 to 6.0, preferably 1.8 to 4.0. In order to have a range of, it is directly polymerized or purchased for use. Alkali-soluble resin having a molecular weight and a molecular weight distribution in the above range can improve the already mentioned hardness, and not only has a high residual film ratio, but also has excellent solubility in non-exposed portions in the developer, The resolution can be improved.

  The alkali-soluble resin is one kind selected from the group consisting of a polymer of a carboxyl group-containing unsaturated monomer, a copolymer with a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof. Including the above.

  In this case, the carboxyl group-containing unsaturated monomer can be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or the like. Specifically, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, phthalate. Examples include acid mono (2-acryloyloxyethyl) and phthalate mono (2-methacryloyloxyethyl). The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used alone or in admixture of two or more.

  Monomers that can be copolymerized with a carboxyl group-containing unsaturated monomer include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, Carboxylic acid vinyl ester compound, unsaturated ether compound, vinyl cyanide compound, unsaturated imide compound, aliphatic conjugated diene compound, giant monomer having monoacryloyl group or monomethacryloyl group at the end of the molecular chain, bulky 1 type chosen from the group which consists of a sex monomer and these combination is possible.

  More specifically, the copolymerizable monomer includes styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxy. Styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene Aromatic vinyl compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl Acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxy Butyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, Benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, Methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, Bornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol Unsaturated carboxylic acid esters such as monoacrylate and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl Methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopro Unsaturated carboxylic acid aminoalkyl ester compounds such as polyacrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate Carboxylic acid vinyl ester compounds such as vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, cyanide Vinyl cyanide compounds such as vinylidene; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylate , Unsaturated amides such as N-2-hydroxyethyl methacrylamide; unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; fats such as 1,3-butadiene, isoprene and chloroprene Giant having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane Monomers: Bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton capable of reducing the non-dielectric constant value can be used. .

  The alkali-soluble resin is 10 to 80 parts by weight, specifically 15 to 70 parts by weight, more specifically 20 to 45 parts by weight with respect to 100 parts by weight as a whole of the solid content of the self-luminous photosensitive resin composition. May be included.

  When the alkali-soluble resin is included in the above range, the solubility in the developer is sufficient, so that pattern formation is easy, and a reduction in the film thickness of the pixel portion of the exposed portion is prevented during development, so that the non-pixel portion This is preferable because the omission of is good. When the alkali-soluble resin is contained in less than the above range, some non-pixel portions may be missing, and when the alkali-soluble resin is contained in excess of the above range, the solubility in the developer is somewhat lowered to form a pattern. Can be somewhat difficult.

  The self-luminous photosensitive resin composition according to the present invention can contain a photopolymerization initiator, and the photopolymerization initiator is not particularly limited as long as it can polymerize the photopolymerizable compound. Can be used without In particular, the photopolymerization initiator is composed of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and a thioxanthone compound in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like. It is preferable to use one or more compounds selected from the group consisting of:

  Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydride). Xyloxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4 -Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl). ) Benzophenone and 2,4,6-trimethylbenzophenone.

  Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6. -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6 (4-Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- ( 4-diethylamino-2-methyl Phenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. .

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3- Dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5' -Tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted with a carboalkoxy group. Of these, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4′5,5′-tetraphenyl-1,2′-biimidazole are preferably used.

  Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and as commercially available products, Irgacure OXE 01 and OXE 02 manufactured by Basf are representative. .

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  The photopolymerization initiator is 0.1 to 10 parts by weight, preferably 1 to 9.5 parts by weight, more preferably 5 to 9 parts by weight based on 100 parts by weight of the total solid content of the self-luminous photosensitive resin composition. .5 parts by weight.

  When the photopolymerization initiator is included in the above range, the self-luminous photosensitive resin composition is highly sensitive and the exposure time is shortened, which is preferable because productivity is improved and high resolution can be maintained. Further, there is an advantage that the strength of the pixel portion formed using the self-luminous photosensitive resin composition according to the present invention and the smoothness on the surface of the pixel portion are improved.

  The photopolymerization initiator may further include a photopolymerization initiation auxiliary agent in order to improve the sensitivity of the self-luminous photosensitive resin composition in the present invention. When the photopolymerization initiation auxiliary agent is contained, there is an advantage that sensitivity is further increased and productivity is improved.

  As the photopolymerization initiation auxiliary agent, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used, but are not limited thereto.

  As the amine compound, an aromatic amine compound is preferably used. Specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, or triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. Ethyl acetate, isoamyl 4-dimethylaminobenzoate, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name) : Michler's ketone), 4,4′-bis (diethylamino) benzophenone, and the like can be used.

  The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy. Examples include phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

  Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), Examples include pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

  The photopolymerization initiation auxiliary agent can be appropriately added and used within a range that does not impair the scope of the present invention.

  The 2nd solvent contained in the self-luminous photosensitive resin composition of this invention is not specifically limited, The organic solvent normally used in the said field | area can be included. The first solvent may be the same as the second solvent, or may be different from each other. However, the second solvent does not include a halogenated hydrocarbon solvent; an aromatic hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent.

  Specific examples of the second solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diester. Diethylene glycol dialkyl ethers such as propyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Alkylene glycol alkyl ether acetates such as cetate; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol, butanol, hexanol, Examples include alcohols such as cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

  The second solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C., more preferably alkylene glycol alkyl ether acetates, ketones, from the viewpoints of coatability and drying properties. Examples include esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxypropionic acid. And methyl. These 2nd solvents can be used individually or in mixture of 2 or more types, respectively.

  The second solvent may be included in an amount of 25 to 90 parts by weight, specifically 30 to 80 parts by weight based on 100 parts by weight of the self-luminous photosensitive resin composition, but is not limited thereto.

  However, when the content of the second solvent is within the above range, it was applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an ink jet. In some cases, the coating property can be improved, which is preferable. When the content of the second solvent is less than the above range, the process may become more difficult as the coating property is somewhat lowered. When the content exceeds the above range, the color formed with the self-light-emitting photosensitive resin composition There may be a problem that the performance of the filter may be somewhat degraded.

  The self-luminous photosensitive resin composition according to the present invention may further include an additive such as an adhesion promoter and a surfactant in order to enhance the coating property or adhesion.

  The adhesion promoter may be added to improve adhesion to the substrate and has a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. Although a silane coupling agent can be included, it is not limited to these. For example, the silane coupling agent may be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy. Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned, and these can be used alone or in combination of two or more.

  When the self-luminous photosensitive resin composition according to the present invention contains the surfactant, there is an advantage that the coating property can be improved. For example, the surfactants are BM-1000, BM-1100 (BM Chemie), Fluoride FC-135 / FC-170C / FC-430 (Sumitomo 3M), SH-28PA / -190 / SZ-6032 (Toray Industries, Inc.) Fluorine-based surfactants such as Silicone) can be used, but are not limited thereto.

  In addition, the self-luminous photosensitive resin composition according to the present invention may further contain an additive such as an antioxidant, an ultraviolet absorber, and an aggregation inhibitor as long as the effects of the present invention are not impaired. Agents can be appropriately added and used by those skilled in the art as long as the effects of the present invention are not impaired. For example, the additive is 0.05 to 10 parts by weight, specifically 0.1 to 10 parts by weight, more specifically 0.1 to 5 parts by weight, based on the total weight of the self-luminous photosensitive resin composition. However, it is not limited to these.

<Color filter>
Still another aspect of the present invention relates to a color filter manufactured using the above-described self-light-emitting photosensitive resin composition.

  The color filter according to the present invention comprises quantum dots; and a first solvent having a dielectric constant of less than 12.0 at 20 ° C .; a halogenated hydrocarbon solvent such as chloroform or dichloromethane; an aromatic such as benzene or toluene Light emission by including a cured product of a self-luminous photosensitive resin composition containing a quantum dot dispersion excellent in dispersibility, which does not contain a hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent such as N-hexane; There is an advantage that it is excellent in the realization of the characteristics, and since there is no solvent harmful to the human body in the quantum dot dispersion body, there is an advantage that it is excellent in terms of environment.

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

  The substrate may be the substrate for the color filter itself, or may be a part where the color filter is located on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate is made of polyethersulfone (PES) or polycarbonate (PC). There may be.

  The pattern layer is a layer containing the self-luminous photosensitive resin composition of the present invention, which is formed by applying the self-luminous photosensitive resin composition, exposing, developing and thermosetting in a predetermined pattern. It may be. The pattern layer can be formed by performing a method generally known in the art.

  The color filter including the substrate and the pattern layer as described above may further include a barrier rib formed between the patterns and may further include a black matrix, but is not limited thereto.

  In addition, a protective film formed on the pattern layer of the color filter may be further included.

  In still another embodiment of the present invention, the color filter may include one or more selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter may include one or more selected from the group consisting of a red pattern layer including red quantum dots according to the present invention, a green pattern layer including green quantum dots, and a blue pattern layer including blue quantum dots. it can. Each of the red pattern layer, the green pattern layer, and the blue pattern layer can emit red light, green light, and blue light when irradiated with light, and the emitted light of the light source is not particularly limited, A light source that emits blue light from the aspect of better color reproducibility can be used.

  The color filter may include only two kinds of pattern layers of a red pattern layer, a green pattern layer, and a blue pattern layer, but is not limited thereto. However, when the color filter includes only two color pattern layers, the pattern layer may further include a transparent pattern layer that does not contain the quantum dot particles.

  When the color filter includes only the pattern layers of the two kinds of colors, a light source that emits light having a wavelength indicating a color other than the two kinds of colors can be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source that emits blue light can be used. In this case, the red quantum dots are red light, and the green quantum dots are green. The transparent pattern layer can emit blue light as blue light from the light source is transmitted as it is.

<Image display device>
Another aspect of the present invention relates to an image display device including the color filter described above.

  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.

  Since the image display device according to the present invention includes a cured product of the self-light-emitting photosensitive resin composition including the quantum dot dispersion having excellent dispersibility, there is an advantage that the light-emitting characteristics are excellent.

  The image display device may further include a light source that emits blue light and a transparent pattern layer, and the above-described content can be applied to the light source that emits blue light and the transparent pattern layer.

  Hereinafter, the present specification will be described in detail with reference to examples. However, the examples according to the present specification may be modified in various other forms, and it is not understood that the scope of the present specification is limited to the examples described in detail below. The examples herein are provided to provide a more thorough explanation of the specification to those having average knowledge in the art. In addition, “%” and “parts” indicating the content are based on weight unless otherwise specified.

Production Example 1: Synthesis of InP / ZnS core-shell quantum dot particles
Preparation of InP Core quantum dots Indium acetate 0.4 mmol (0.058 g), palmitic acid 0.6 mmol (0.15 g), 1-octadecene 20 mL were placed in a reactor and vacuumed. The bottom was heated at 120 ° C. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating at 280 ° C., a mixed solution of tris (trimethylsilyl) phosphine (TMS3P) 0.2 mmol (58 uL) and trioctylphosphine 1.0 mL was rapidly injected and allowed to react for 20 minutes. Acetone was added to the reaction solution rapidly cooled to room temperature, and the precipitate obtained by centrifugation was dispersed in toluene. The obtained InP semiconductor nanocrystal exhibits a UV first absorption maximum wavelength of 560 to 590 nm.

Preparation of InP / ZnS core-shell quantum dots Zinc acetate 2.4 mmol (0.448 g), oleic acid 4.8 mmol, and trioctylamine 20 mL were placed in a reactor and heated at 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen, and the temperature of the reactor was raised to 280 ° C. After adding 2 ml of the previously synthesized InP core solution and then 4.8 mmol of S / TOP, the final mixture was allowed to react for 2 hours. Ethanol was added to the reaction solution rapidly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain InP / ZnS core-shell quantum dots.
The photoluminescence spectrum of the obtained nanoquantum dot was 635 nm.

Production Example 2: Synthesis of alkali-soluble resin, a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube was prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, After adding 10 parts by weight of cyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), the mixture was stirred and mixed. Prepared, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90 ° C. while stirring. Next, dropping of the monomer and chain transfer agent from the dropping funnel was started. The dropwise addition proceeds for 2 hours each while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours, and then a gas introduction pipe was introduced to introduce oxygen / nitrogen = 5/95 (v / V) Bubbling of the mixed gas was started. Next, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 part by weight of triethylamine were charged into the flask, and the mixture was heated at 110 ° C. for 8 parts. The reaction was continued for a time, and then cooled to room temperature to obtain an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g.

Production Example 3: Production of Quantum Dot Dispersion A quantum dot dispersion (A ′) was produced with the composition shown in Table 1 below, and the first solvents were as shown in Table 2 below.

Examples and Comparative Examples: Manufacture of Self-Luminescent Photosensitive Resin Compositions Self-luminous photosensitive resin compositions according to Examples and Comparative Examples were manufactured with the compositions according to Table 3 below.

Production of Color Filter (Glass Substrate) A color filter was produced using the self-luminous photosensitive resin composition produced according to the above Examples and Comparative Examples. Specifically, each self-luminous photosensitive resin composition is applied onto a glass substrate by a spin coating method, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. It was. Next, a test photomask having a regular square transmission pattern of horizontal × vertical 20 mm × 20 mm and a line / space pattern of 1 μm to 100 μm is placed on the thin film, and the distance between the test photomask and the test photomask is 100 μm. Irradiated. 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. Was not used. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 80 seconds. 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.

Experimental Example (1) Measurement of Dispersion Particle Size of Quantum Dot Dispersion and Self-Luminescent Photosensitive Resin Composition The dispersion particle size was measured using ELSZ-2000ZS (manufactured by Otsuka Co., Ltd.), and is shown in Table 4 below. In general, when the quantum dot particles are aggregated, the dispersion particle size is increased, which can cause a problem that the light emission characteristics are lowered.

(2) Measurement of light emission intensity (photoluminescence intensity) A 365 nm type 4W UV irradiator (VL-4LC, VILBER) is formed on a pattern portion formed by a regular square pattern of 20 mm × 20 mm among the color filters in which self-luminous pixels are formed. The region subjected to light conversion was measured using LOURMAT), and the light emission intensity after light conversion was measured using Spectrum meter USB2000 + (manufactured by Ocean Optics). It can be judged that the higher the measured light emission intensity (photoluminescence intensity), the more excellent self-luminous properties are exhibited, and the measurement results of the light emission intensity are shown in Table 4 below.

  As can be seen from Table 4, a quantum dot dispersion having excellent photoluminescence (photoluminescence) quantum efficiency as well as excellent dispersion characteristics by using a solvent having a dielectric constant of less than 12 when the quantum dot dispersion is produced. Was available.

Claims (9)

A first solvent having a dielectric constant less than 12.0 at 20 ° C .;
However, a quantum dot dispersion not containing a halogenated hydrocarbon solvent; an aromatic hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent.   The quantum dot dispersion according to claim 1, wherein the first solvent has a dielectric constant of less than 8.0 at 20 ° C.   The quantum dot dispersion according to claim 2, wherein the first solvent has a dielectric constant of less than 6.0 at 20 ° C.   The first solvent is methyl isoamyl ketone, diisobutyl ketone, diethyl carbonate, butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl isobutyrate, 2-ethylhexyl acetate, hexyl acetate, neryl acetate, dipropylene glycol dimethyl ether and dipropylene glycol methyl Ether acetate, ethyl o-formate, ethyl butyrate, diethyl acetal, methyl hexanoate, methyl octanoate, ethyl isovalerate, methyl 3-methyl butanoate, isopentyl 3-methyl butanoate, isopentyl butano Ate, ethyl methyl carbonate, pentyl pentanoate, isoamyl propionate, isobutyl isovarate, propyl isovale 2- (2- (vinyloxy) ethoxy) propane, 1-allyloxy-2-isopropoxy-ethane, (2-isobutoxy-ethoxy) -ethene, 1-vinyloxy-2-isopentoxy-ethane, 1-vinyloxy- The quantum dot dispersion according to claim 1, comprising one or more selected from the group consisting of 2-pentoxy-ethane.   The quantum dot dispersion according to claim 1, wherein the quantum dot dispersion further includes one or more selected from the group consisting of a phosphate ester dispersant, an acrylic dispersant, and a urethane dispersant. A self-luminous photosensitive composition comprising at least one selected from the group consisting of the quantum dot dispersion according to any one of claims 1 to 5; and a photopolymerizable compound; an alkali-soluble resin; a photopolymerization initiator; and a second solvent. Resin composition.   The self-luminous photosensitive resin composition according to claim 6, wherein the quantum dot dispersion is contained in an amount of 3 to 80 parts by weight with respect to 100 parts by weight of the self-luminous photosensitive resin composition as a whole.   A color filter comprising a cured product of the self-luminous photosensitive resin composition according to claim 6.   An image display device comprising the color filter according to claim 8.