WO2018074726A1 - Quantum dot dispersion, spontaneous emission photosensitive resin composition containing same, color filter manufactured using same, and image display device - Google Patents

Abstract

According to the present invention, a quantum dot dispersion comprises: a quantum dot; and a first solvent having a dielectric constant less than 12.0 at 20°C, but does not comprise a halogenated hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, and an aliphatic saturated hydrocarbon-based solvent.

Description

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

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

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units. The size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment-dispersible photosensitive resin has been applied, but a part of the light is absorbed by the color filter while the light emitted from the light source passes through the color filter. The problem is that the efficiency is lowered and the color reproduction is lowered 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 excellent performance such as high brightness and high contrast ratio are required. A color filter manufacturing method using the self-luminous photosensitive resin composition containing is proposed.

The quantum dots included in the self-luminous photosensitive resin composition are generally purchased and used in commercially available forms, and these quantum dots are dispersed and sold in non-polar solvents harmful to the human body, such as chloroform, toluene, n-hexane, or benzene. Solvents described above are highly volatile compounds (Volatile Organic Compound) or carcinogenic, neurotoxic, and have a high risk of abnormal reproductive function.

Korean Patent Application Publication No. 2015-0034013 relates to a quantum dot-resin nanocomposite and a method for manufacturing the same, and discloses a content related to a quantum dot-resin nanocomposite in which a curable resin and a plurality of quantum dots form nanoparticles.

Korean Patent Laid-Open No. 2016-0069393 relates to a method for manufacturing a light conversion composite, a light conversion composite, a light conversion film, a backlight unit, and a display device including the same, including a matrix resin; And a quantum dot-polymer bead dispersed in the matrix resin, wherein the light conversion composite has scattering intensity according to a wave number measured by Small Angle X-ray Scattering. Disclosed is a light conversion composite material having a wave number q of a peak point of an intensity graph of 0.0056 Å ⁻¹ to 0.045 Å ⁻¹ .

In the case of the above documents, a solvent harmful to the human body is used as the solvent, or because the patterning is not performed because the dispersion property is not excellent, there is a problem that it cannot be applied for a color filter.

Therefore, development of a quantum dot dispersion and a self-luminous photosensitive resin composition which are excellent in dispersibility and capable of realizing excellent luminescent properties without containing components harmful to a human body are required.

[Preceding technical literature]

[Patent Documents]

Republic of Korea Patent Publication No. 2015-0034013 (2015.04.02.)

Republic of Korea Patent Publication No. 2016-0069393 (2016.06.16.)

An object of the present invention is to provide a quantum dot dispersion containing no solvent harmful to a human body, and a self-luminous photosensitive resin composition comprising the same.

In addition, the present invention is to provide a quantum dot dispersion having excellent dispersibility and excellent light emission characteristics, a self-luminous photosensitive resin composition comprising the same.

In addition, an object of the present invention is to provide a color filter and an image display device having excellent light emission characteristics manufactured by using the aforementioned quantum dot dispersion and a self-luminous photosensitive resin composition.

A quantum dot dispersion according to the present invention for achieving the above object is a quantum dot; And a first solvent having a dielectric constant of less than 12.0 at 20 ° C., including a halogenated hydrocarbon solvent; Aromatic hydrocarbon solvents; And aliphatic saturated hydrocarbon solvents.

In addition, the present invention is a quantum dot dispersion described above; And photopolymerizable compounds; Alkali-soluble resins; Photopolymerization initiator; And it provides a self-luminous photosensitive resin composition further comprising one or more selected from the group consisting of a second solvent.

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

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

Since the quantum dot dispersion according to the present invention and the self-luminous photosensitive resin composition including the same include a solvent having a specific dielectric constant, there is an advantage of excellent dispersibility and excellent light emission characteristics, and does not contain a human toxic substance. There is an advantage.

In addition, the color filter and the image display device made of the self-luminous photosensitive resin composition according to the present invention has an advantage of excellent light emission characteristics.

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

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

<Quantum dot dispersion>

One aspect of the invention relates to a quantum dot dispersion. Specifically, one aspect of the present invention is a quantum dot; And a first solvent having a dielectric constant of less than 12.0 at 20 ° C., including a halogenated hydrocarbon solvent; Aromatic hydrocarbon solvents; And an aliphatic saturated hydrocarbon solvent; relates to a quantum dot dispersion not containing.

The quantum dot dispersion according to the present invention includes a quantum dot. The quantum dots may refer to nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters that form nanoparticles, which are called quantum dots when they are semiconducting. When the quantum dots reach the excited state from the outside, the quantum dots emit energy according to their corresponding energy bandgap.

The color filter made of the self-luminous photosensitive resin composition according to the present invention can emit light (light luminescence) by light irradiation by including the quantum dots.

In a typical image display apparatus including a color filter, white light is transmitted through the color filter to implement color. In this process, a part of the light is absorbed by the color filter, thereby degrading light efficiency. However, in the case of including the color filter made of the self-luminous photosensitive resin composition according to the present invention, since the color filter is self-luminous by the light of the light source, it is possible to implement more excellent light efficiency, and also emit light with color Since the color reproducibility is excellent, and the light is emitted in all directions by the photoluminescence, the viewing angle is also improved.

It will not specifically limit, if it is a quantum dot particle which can emit light by stimulation by light. For example, group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; And it can be selected from the group consisting of these, these can be used alone or in combination of two or more.

Specifically, the II-VI semiconductor compound may be 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, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And an elemental compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, 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; Three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; And an elemental compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and mixtures thereof.

The Group IV-VI semiconductor compound may be selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and one or more selected from the group consisting of an elemental compound selected from the group consisting of mixtures thereof, but are not limited thereto.

Although not limited thereto, the group IV element or a compound including the same may include an element compound selected from the group consisting of Si, Ge, and mixtures thereof; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The quantum dots are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.

Specifically, in the dual structure of the core-shell, the material constituting each core and shell may be made of the above-mentioned different semiconductor compounds. For example, the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include one or more materials 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 a part of the surface is substituted with an organic ligand, but is not limited thereto. The organic ligand is preferably bonded to the surface of the quantum dot to play a role of stabilizing the quantum dot. The organic ligand is not limited in the present invention, but C5 to C20 alkyl carboxylic acid, alkenyl carboxylic acid or alkynyl carboxylic acid; Pyridine; Mercapto alcohol; Thiols; Phosphine; Phosphine oxides; Primary amine; Secondary amines; And the like.

The method of replacing a part of the surface of the quantum dot with an organic ligand is not limited in the present invention, and conventional methods performed in the art may be used.

The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD), or a molecular beam epitaxy (MBE), but are not limited thereto. .

The wet chemical process is a method of growing a particle by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Therefore, the nano solvent is easier and cheaper than the vapor deposition method such as the organometallic chemical vapor deposition process or molecular beam epitaxy. Since the growth of the particles can be controlled, it is preferred to produce the quantum dots according to the invention using the wet chemical process.

The quantum dot may be included in 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 quantum dot dispersion solids. When the quantum dot is included in the above range, it is possible to provide a self-luminous photosensitive resin composition having excellent photosensitivity. When the quantum dot is included in the range below the photosensitive properties may be slightly reduced, and when included in excess of the above range, the content of the other components, such as alkali-soluble resin, photopolymerizable compound to be described later in contrast to the quantum dot Since it is relatively small, there is a problem that the manufacture of the color filter may be somewhat difficult, so it is preferably included within 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 is a halogenated hydrocarbon solvent; Aromatic hydrocarbon solvents; And aliphatic saturated hydrocarbon solvents.

The halogenated hydrocarbon solvent may include, but is not limited to, for example, chloroform, dichloromethane, methylene chloride tetrachloride, dichloroethane, tetrachloroethane, and the like.

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

The aliphatic saturated hydrocarbon solvent may include, but is not limited to, chain alkanes such as N-hexane, pentane, heptane, cyclic alkanes such as cyclopentane, cyclohexane, kerosene, and the like.

Specifically, the first solvent according to the present invention may be a halogenated hydrocarbon solvent such as chloroform or dichloromethane; Aromatic hydrocarbon solvents such as benzene or toluene; Or an aliphatic saturated hydrocarbon solvent such as N-hexane; the content of 100 ppm. Specifically, it may be 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 can protect the worker from potential danger.

In another embodiment of the present invention, the first solvent may be a dielectric constant of less than 8.0 at 20 ℃.

In another embodiment of the present invention, the first solvent may be a dielectric constant of less than 6.0 at 20 ℃.

The quantum dot dispersion according to the present invention has an advantage of excellent quantum dot dispersion characteristics by including a first solvent satisfying the dielectric constant value. For this reason, the color filter and the image display apparatus made of the self-luminous photosensitive resin composition including the quantum dot dispersion according to the present invention has an advantage of excellent light emission characteristics.

When the dielectric constant of the first solvent is 12.0 or more at 20 ° C., the dispersibility of the quantum dots is somewhat lowered, and thus, the phenomenon of aggregation of the quantum dots may occur, thereby reducing the overall luminescence properties, and the color filter having nonuniform performance is manufactured. As such, it is preferable to use a first solvent having a dielectric constant of less than 12.0 at 20 ° C.

In another embodiment of the 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, isopentyl butanoate, ethyl methyl carbonate, pentyl pentanoate, isoamyl propionate, isobutyl isovalerate, propyl isovalerate, 2- ( 2- (vinyloxy) ethoxy) propane, 1-allyloxy-2-isoproxy-ethane, (2-isobutoxy-ethoxy) And at least one selected from the group consisting of -ethene, 1-vinyloxy-2-isopentoxy-ethane, and 1-vinyloxy-2-pentoxy-ethane.

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 based on 100 parts by weight of the total quantum dot dispersion. When the first solvent is included in the range based on 100 parts by weight of the total quantum dot dispersion, it is preferable to improve the dispersibility of the quantum dot. When the first solvent is included in the less than the above range, the optical properties are advantageous, but the dispersion properties may be slightly lowered. When the first solvent is exceeded, the dispersion properties are advantageous, but the optical properties may be slightly lowered, thus satisfying the above range. It is preferable.

In 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-based dispersant, an acrylic dispersant and a urethane-based dispersant.

When the quantum dot dispersion further comprises one or more selected from the group consisting of the phosphate ester-based dispersant, the acrylic dispersant and the urethane-based dispersant, the dispersibility of the quantum dot and the first solvent is improved, thereby providing excellent quantum efficiency.

The phosphate ester-based dispersant may include a phosphate ester-based compound, wherein the phosphate ester-based compound is a hydroxy group or a hydroxy group present in phosphate ester ((HO) ₂ PO (OR)) or phosphoric acid (H ₃ PO ₄ ) The hydrogen atom may be substituted or unsubstituted with another functional group. For example, the phosphate ester compound may be represented in the form of (H ₂ PO ₃ −), but is not limited thereto. In the present invention, the "phosphate ester type" may 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 includes the phosphate ester compound, there is an advantage in that the light efficiency and the photosensitive characteristics can be suppressed.

The phosphate ester compound may further include at least one of a polyether moiety, a polyester moiety, and a phosphate group in one molecule.

In the present invention, "poly-" may refer to a compound composed of a large number of repeating units, and the "polyether portion" and "polyester portion" may have 1 to 20 repeating units each containing an ether group or an ester group. It can be referred to as a part consisting of. Preferably, in the present invention, the repeating unit may be composed of 5 to 20, more preferably 10 to 20, in this case there is an excellent compatibility.

When the phosphate ester compound further includes a polyether moiety in one molecule, compatibility with alkali-soluble resins to be described later is improved, and the phosphate ester compound further includes a polyester moiety in one molecule. There is an advantage that the compatibility with the alkali-soluble resin and the dissolution characteristics for the alkaline developer are improved. When the phosphate ester compound further includes a phosphate group in one molecule, the phosphate ester compound may serve as a protective layer through adsorption on the surface of the quantum dot, and has the advantage of deagglomerating the quantum dot.

Preferably, the phosphate ester compound according to the present invention may include a polyether moiety, a polyester moiety, and a phosphate group in one molecule, in which case deagglomeration of quantum dots reduces the particle size of the dispersion, and compatibility with alkali-soluble resins. And dissolution properties in alkaline developing solution, which is advantageous because it has an advantageous advantage in pattern formation.

In the present invention, the "acid value" is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer and may be involved in solubility in the self-luminous photosensitive resin composition described later. When the acid value of the phosphate ester compound is 10 (KOHmg / g) or more, specifically 10 to 200 (KOHmg / g) is preferable in view of the development rate of the self-luminous photosensitive resin composition containing the dispersant. When the acid value is less than the above range, it may be somewhat difficult to secure a sufficient developing speed, and when the acid value exceeds the above range, adhesion to the substrate may be reduced, thereby causing short circuiting of the pattern, and lowering the storage stability of the overall composition to increase the viscosity. Since the problem may occur, it is preferable to satisfy the above range.

An acrylic block copolymer is mentioned as said acrylic dispersing agent. As an acryl-type block copolymer, the block copolymer which has the block containing a basic group and an acidic group, and the block which does not contain the said basic group or the said acidic group is preferable.

The basic group and the acid group (hereinafter, these groups may be collectively referred to as "quantum dot adsorber") each exhibit an action of adsorbing the quantum dots described above.

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

As a monomer which has the said basic group, the monomer which has a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group is mentioned. Specific examples of the monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, diethylacrylamide, and dimethylaminopropyl Methacrylamide, acryloyl morpholine, vinylimidazole, 2-vinylpyridine, monomers having an amino group and a caprolactone skeleton; A reaction product of a compound having a glycidyl group such as glycidyl (meth) acrylate with a compound having one secondary amino group in a molecule thereof; (Meth) acryloylalkyl isocyanate compound with 4- (2-aminomethyl) -pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-hydroxyethyl) pyridine, 1- (2-aminoethyl ) -Piperazine, 2-amino-6-methoxybenzothiazole, 1- (2-hydroxyethylimidazole), N, N-diallylmelamine, N, N-dimethyl-1,3-propanediamine And reactants with each other.

As a monomer which has the said acid group, the monomer which has a carboxy group and a sulfo group is mentioned. As a monomer which has a carboxy group, 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; Etc. can be mentioned. 2-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, styrenesulfonic acid, etc. are mentioned as a monomer which has a sulfo group.

As a block which does not contain the said quantum dot adsorption agent, Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, vinyltoluene, and benzyl chloride; Unsaturated carboxylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate; Unsaturated carboxylic acid arylalkyl esters such as benzyl (meth) acrylate; The block derived from a polycaprolactone containing compound, a polyalkylene glycol monoester type compound, etc. are mentioned.

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

The amine titer of the said acryl-type block copolymer is 0-200 mgKOH / g normally, Preferably it is 0-120 mgKOH / g, More preferably, it is 0-80 mgKOH / g.

As a commercial item of the said acryl-type block copolymer, "Disperbyk (trademark) -112 (amine value 36 mgKOH / g)" and "Disperbyk (registered trademark) -2000 (amine value 4 mgKOH / g) manufactured by BIC Chemie Japan Co., Ltd. were manufactured. "Disperbyk-2001 (amine value 29 mgKOH / g)", "Disperbyk (registered trademark) -2020 (amine value 38 mgKOH / g)", "Disperbyk (registered trademark) -2050 (amine value 30 mgKOH / g)", " Disperbyk (R) -2070 (amine value 20 mgKOH / g) ”and the like.

As the urethane-based dispersant, a dispersant obtained by reacting a compound having a number-average molecular weight of 300 to 10,000 with one or more hydroxyl groups in a molecule and a basic group-containing compound having a functional group capable of reacting with an isocyanate group in the molecule, isocyanate group of a polyisocyanate compound Can be.

As a method of obtaining such a urethane type dispersing agent, the method etc. which are described in Unexamined-Japanese-Patent No. 60-166318 can be used.

As said polyisocyanate compound, the isocyanate compound which has two or more isocyanate groups is mentioned,

Dimer of 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Aromatic diisocyanate compounds such as 1,5-naphthylene diisocyanate and 3,3'-dimethylbiphenyl-4,4'-diisocyanate;

Hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanate methylene) cyclohexane, etc. Aliphatic polyisocyanates and alicyclic polyisocyanates;

Polyisocyanate having isocyanuric groups derived from the diisocyanate (polyisocyanate having an isocyanuric group formed by trimming the diisocyanate);

Polyisocyanate obtained by reacting diisocyanate with a polyol;

Polyisocyanate obtained by the biuret reaction of a diisocyanate compound; Etc. can be mentioned.

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

As a compound which has one or more hydroxyl groups in the said molecule | numerator, a polyether compound, a polyester compound, etc. are mentioned.

As said polyether compound, Polyalkylene glycol, such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol;

Alkylene glycols such as ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, ditrimethylolpropane, dipentaerythritol ;

Modified products of low molecular weight monools, such as methanol and ethanol, etc. are mentioned.

Examples of the modified substances of the low molecular monools include ethylene oxide modified substances, propylene oxide modified substances, butylene oxide modified substances, tetrahydrofuran modified substances and the like.

Examples of the polyester compound include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, ditrimethylol propane, dipenta Modified products of alkylene glycols such as erythritol;

Modified substances of low molecular weight monools such as methanol and ethanol;

Esterified products of aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol, that is, aliphatic polyester polyols;

Esterified products of aromatic dicarboxylic acids such as terephthalic acid with polyols such as neopentyl glycol, that is, polyester polyols (such as aromatic polyester polyols);

Polyhydric hydroxy group compounds such as polycarbonate polyol, acryl polyol, polytetramethylenehexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid Esterified products with dicarboxylic acids such as;

Polyhydric hydroxy group-containing compounds such as monoglycerides obtained by transesterification of polyhydric hydroxy group-containing compounds such as glycerin and fatty acid esters;

Etc. can be mentioned.

Examples of modified substances of alcohols such as alkylene glycols and low molecular weight monools include ε-caprolactone modified substances, γ-butyrolactone modified substances, δ-valerolactone modified substances, and methylvalerolactone modified substances. have.

Among the compounds having at least one hydroxyl group in the molecule, ε-caprolactone adducts of alcohols are preferable.

The number average molecular weight of the compound which has one or more hydroxyl groups in the said molecule | numerator is 300-10,000, Preferably it is 300-6,000.

In addition, a number average molecular weight and a weight average molecular weight can be measured by a column chromatography method.

It does not specifically limit as a basic group containing compound which has a functional group which can react with an isocyanate group in the said molecule, The compound normally used in the technical field of a dispersing agent can be used.

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

Such basic group-containing compounds include N, N-dimethyl-1,3-propanediamine, N, N-diethyl1,4-butanediamine, 2-dimethylaminoethanol, 1- (2-aminoethyl) -Piperazine, 2- (1-pyrrolidyl) -ethylamine, 4-amino-2-methoxypyrimidine, 4- (2-aminoethyl) -pyridine, 1- (2-hydroxyethyl) -pipe Razine, 4- (2-hydroxyethyl) -morpholine, 2-mercaptopyrimidine, 2-mercaptobenzoimidazole, 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. Among them, amines having a heterocyclic nitrogen atom are preferable.

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

The amine titer of the said urethane type dispersing agent becomes like this. Preferably it is 0-200 mgKOH / g, More preferably, it is 0-120 mgKOH / g, More preferably, it is 0-80 mgKOH / g. Moreover, it is preferable that it is 0-55 mgKOH / g, and, as for the amine titer of the said urethane type dispersing agent, it is more preferable that it is 5-40 mgKOH / g.

As a commercial item of the said urethane-type dispersing agent, Disperbyk-161 (Amine value 11 mgKOH / g, Big Chem Corporation make), Disperbyk-162 (Amine value 13 mgKOH / g Big Chemistry company make), Disperbyk-167 (Amine value 13 mgKOH / g, Big Chemistry company make) And Disperbyk-182 (amine value 13 mgKOH / g, manufactured by BIC Chem).

In the present specification, the amine number means the amine value per 1 g of the solid content of the dispersant, and using a 0.1 mol / l hydrochloric acid aqueous solution, a potentiometric titration method [for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK-900) ), Manufactured by Hiranumasan Co., Ltd., and then converted into equivalents of potassium hydroxide.

The dispersant may be included in an amount of 1 to 250 parts by weight based on 100 parts by weight of the total quantum dot solids, preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight. When the dispersant is included in the above range is excellent in the deagglomeration effect of the quantum dot, it is possible to suppress the precipitation phenomenon by the polarity difference in the quantum dot dispersion according to the present invention and the self-luminous photosensitive resin composition comprising the same, manufacturing a color filter It is preferable because it can act as a protective layer of the quantum dots in the process.

<Self-luminous photosensitive resin composition>

Another aspect of the present invention is a quantum dot dispersion described above; And photopolymerizable compounds; Alkali-soluble resins; Photopolymerization initiator; And it is related with the self-luminous photosensitive resin composition containing 1 or more types chosen from the group which consists of a 2nd solvent.

In 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 10 to 60 parts by weight based on 100 parts by weight of the total self-luminous photosensitive resin composition. May be included as a wealth. When the self-luminous photosensitive resin composition according to the present invention includes the quantum dot dispersion described above within the above range, there is an advantage in that a color filter having excellent luminescence properties can be manufactured. If the quantum dot dispersion is included in less than the above range, the light emission characteristics may be slightly lowered. If the quantum dot dispersion is included in the above range, the formation of a pattern may be somewhat difficult as the content of the other composition is reduced, and reliability Since it may be lowered, it is preferable to be included in the above range.

The self-luminous photosensitive resin composition according to the present invention may include a photopolymerizable compound. The photopolymerizable compound contained in the self-luminous photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The kind of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acryl The rate, N-vinylpyrrolidone, etc. are mentioned.

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

The kind of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, and propoxylated trimethylolpropane tree (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

Commercially available examples of the photopolymerizable compound include, but are not limited to, A9550 manufactured by Shin-Nakamura Corporation.

The photopolymerizable compound may be included in an amount of 5 to 50 parts by weight, specifically 15 to 45 parts by weight, and more specifically 20 to 37 parts by weight based on 100 parts by weight of the total solid of the self-luminous photosensitive resin composition. When the photopolymerizable compound is included in the above range, there is a preferable advantage in terms of intensity or smoothness of the pixel portion.

When the photopolymerizable compound is included in the range below, the intensity of the pixel portion may be lowered slightly, and when the photopolymerizable compound is included in the above range, smoothness may be slightly lowered, so it is preferably included within the range. .

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

The alkali-soluble resin may serve to make the non-exposed part of the color filter made of the self-luminous photosensitive resin composition alkali-soluble and to remove it, and to leave the exposure area. In addition, when the self-luminous photosensitive resin composition includes the alkali-soluble resin, the quantum dots may be evenly dispersed in the composition, and may serve to maintain the brightness by protecting the quantum dots during the process.

The alkali-soluble resin according to the present invention can be selected to have an acid value of 50 to 200 (KOHmg / g). In addition, the alkali-soluble resin may consider the limitation of the molecular weight and the molecular weight distribution (Mw / Mn) in order to improve the surface hardness for use as a color filter. Preferably, the weight average molecular weight is 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 so as to directly polymerize or purchase and use. Alkali-soluble resins having a molecular weight and molecular weight distribution in the above range can be improved in the hardness already mentioned, as well as high residual film ratio, solubility of the non-exposed portion in the developing solution can be excellent and the resolution can be improved.

The alkali-soluble resin includes at least one member selected from the group consisting of polymers of carboxyl group-containing unsaturated monomers, copolymers with monomers having unsaturated bonds copolymerizable therewith, and combinations thereof.

In this case, the carboxyl group-containing unsaturated monomer may be unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, or the like. Specifically, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. Moreover, unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) And phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) and the like. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

In addition, monomers copolymerizable with carboxyl group-containing unsaturated monomers 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 compounds, unsaturated ether compounds, vinyl cyanide compounds, One type selected from the group consisting of an unsaturated imide compound, an aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or a monomethacryloyl group at the terminal of the molecular chain, a bulky monomer, and a combination thereof is possible.

More specifically, the copolymerizable monomer may be styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxy styrene, 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 Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, 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 meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) a Relate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters of; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acids such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Macromonomers having; Bulky monomers, such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton, can lower the dielectric constant.

The alkali-soluble resin may be included in 10 to 80 parts by weight, specifically 15 to 70 parts by weight, and more specifically 20 to 45 parts by weight based on 100 parts by weight of the total solids of the self-luminous photosensitive resin composition.

When the alkali-soluble resin is included in the above range, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the dropping of the non-pixel portion is good, which is preferable. If the alkali-soluble resin is included in less than the above range, the non-pixel portion may be somewhat missing, and when the alkali-soluble resin is included in more than the above range, the solubility in the developing solution is slightly lowered may be somewhat difficult to form a pattern.

The self-luminous photosensitive resin composition according to the present invention may include a photopolymerization initiator, and the photopolymerization initiator may be used without particular limitation as long as it can polymerize the photopolymerizable compound. In particular, the photopolymerization initiator is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and a thioxanthone compound in terms of polymerization properties, start efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl 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] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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-methylphenyl) 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-dichloro Phenyl) -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, The imidazole compound etc. which the phenyl group of a 4'5,5'- tetraphenyl- 1,2'- biimidazole or a 4,4 ', 5,5' position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and commercially available BASF Irgacure OXE 01 and OXE 02 are typical examples.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.

The photopolymerization initiator may be included in an amount of 0.1 to 10 parts by weight, preferably 1 to 9.5 parts by weight, and more preferably 5 to 9.5 parts by weight based on 100 parts by weight of the total solid of the self-luminous photosensitive resin composition.

In the case where the photopolymerization initiator is included in the above range, the self-luminous photosensitive resin composition may be highly sensitive, and thus the exposure time may be shortened, so that productivity may be improved and high resolution may be maintained. Moreover, there exists an advantage that the intensity | strength of the pixel part formed using the self-luminous photosensitive resin composition concerning this invention, and smoothness in the surface of the said pixel part become favorable.

The photopolymerization initiator may further include a photopolymerization initiation aid in order to improve the sensitivity of the self-luminous photosensitive resin composition in the present invention. When the photopolymerization start adjuvant is included, there is an advantage in that the sensitivity is higher and the productivity is improved.

The photopolymerization initiation assistant may be preferably used, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, 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, dimethoxyphenylthioacetic acid, Chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.

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

The second solvent included in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and may include an organic solvent commonly used in the art. The first solvent may be the same as the second solvent, or may be different from each other. However, the second solvent may be a halogenated hydrocarbon solvent; Aromatic hydrocarbon solvents; And aliphatic saturated hydrocarbon solvents.

Specifically, the second solvent is ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Diethylene glycol dialkyl ethers such as ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

In view of applicability and dryness, the second solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in the second solvent, more preferably alkylene glycol alkyl ether acetates, ketones, or 3 Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-ethoxypropionate ethyl and 3-meth Methyl oxypropionate etc. are mentioned. 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 total self-luminous photosensitive resin composition, but is not limited thereto.

However, when the content of the second solvent is included within the above range, the coating property when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, etc. It is preferable because it can become good. If the content of the second solvent is less than the above range, the process may be somewhat difficult as the applicability is slightly lowered. If the second solvent exceeds the above range, the performance of the color filter formed of the self-luminous photosensitive resin composition may be slightly lowered. This can cause problems.

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

The adhesion promoter may include a silane coupling agent having a reactive substituent selected from the group consisting of carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups, and combinations thereof, which may be added to increase adhesion to the substrate. It is not limited. For example, the silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-glycidoxy If propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, these can be used individually and in combination of 2 or more types.

When the self-luminous photosensitive resin composition according to the present invention includes the surfactant, there is an advantage that the coating property can be improved. For example, the surfactant is BM-1000, BM-1100 (BM Chemie Co., Ltd.), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ-6032 (Dore Siri). Fluorine-based surfactants such as Corn Co., Ltd. may be used, but is not limited thereto.

In addition, the self-luminous photosensitive resin composition according to the present invention may further include additives such as antioxidants, ultraviolet absorbers and anti-agglomerating agents in a range that does not impair the effects of the present invention, the additives also inhibit the effects of the present invention It can be used by those skilled in the art as long as it does not. For example, the additive may be used in an amount of 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, but is not limited thereto.

<Color filter>

Yet another aspect of the present invention relates to a color filter manufactured using the above-described self-luminous photosensitive resin composition.

Color filter according to the present invention is a quantum dot; And a first solvent having a dielectric constant of less than 12.0 at 20 ° C .; and a halogenated hydrocarbon solvent such as chloroform or dichloromethane; Aromatic hydrocarbon solvents such as benzene or toluene; And a cured product of a self-luminous photosensitive resin composition including a quantum dot dispersion having excellent dispersibility, which does not include an aliphatic saturated hydrocarbon-based solvent such as N-hexane. Since there is no solvent harmful to the human body in the environment there is an excellent advantage.

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

The substrate may be the substrate of the color filter itself, or may be a portion where the color filter is positioned in 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 may be polyethersulfone (PES) or polycarbonate (PC).

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

The color filter including the substrate and the pattern layer may further include a partition formed between each pattern, 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 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 a red quantum dot, a green pattern layer including a green quantum dot, and a blue pattern layer including a blue quantum dot according to the present invention. . The red pattern layer, the green pattern layer, and the blue pattern layer may respectively emit red light, green light, and blue light when irradiated with light. In this case, the emission light of the light source is not particularly limited, but blue light may be generated in terms of better color reproducibility. A light source that emits can be used.

The color filter may include only a pattern layer of two colors among the red pattern layer, the green pattern layer, and the blue pattern layer, but is not limited thereto. However, when the color filter includes only the pattern layer of two colors, the pattern layer may further include a transparent pattern layer containing no quantum dot particles.

When the color filter includes only the pattern layers of the two colors, a light source emitting light having a wavelength representing a color other than the two colors may be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source emitting blue light may be used. In this case, red quantum dots emit red light and green quantum dots emit green light, and the transparent pattern layer may As the blue light transmitted by the light source is transmitted as it is, blue can be obtained.

<Image display device>

Moreover, another aspect of this invention is related with the image display apparatus containing the color filter mentioned above.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

Since the image display apparatus which concerns on this invention contains the hardened | cured material of the self-luminous photosensitive resin composition containing the quantum dot dispersion excellent in dispersibility, there exists an advantage which is excellent in luminescence characteristic.

The image display apparatus may further include a light source emitting blue light and a transparent pattern layer, and the above-described information may be applied to the light source emitting blue light and the transparent pattern layer.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Production Example  One: InP Of ZnS  Core-shell Quantum dots  Synthesis of Particles

InP  Core Quantum dots  Produce

0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid and 20 mL of 1-octadecene were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen. After heating to 280 ° C., a mixed solution of 0.2 mmol (58 uL) of tris (trimethylsilyl) phosphine (TMS3P) and 1.0 mL of trioctylphosphine was rapidly injected and reacted for 20 minutes. Acetone was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was dispersed in toluene. The obtained InP semiconductor nanocrystal shows a UV first absorption maximum wavelength of 560 to 590 nm.

InP Of ZnS  Core-shell Quantum dots  Produce

2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid, 20 mL of trioctylamine were placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour the atmosphere in the reactor was switched to nitrogen and the reactor was heated to 280 degrees. 2 ml of the synthesized InP core solution was added thereto, followed by 4.8 mmol of S / TOP, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution cooled to room temperature rapidly, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain an InP / ZnS core-shell quantum dot.

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, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl 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) were added thereto, stirred and mixed to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanethiol. 24 parts by weight of PGMEA was added thereto, followed by stirring and mixing to prepare a lot of chain transfer agent dropping lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition proceeds for 2 hours each while maintaining 90 ° C, and after 1 hour, the temperature is raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube is introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. The ring started. Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were added to the flask, followed by 8 hours at 110 ° C. The reaction was continued and an alkali-soluble resin having a solid content of 29.1 wt%, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g was then cooled to room temperature.

Production Example  3: Quantum dots Dispersion  Produce

To prepare a quantum dot dispersion (A ') in the composition of Table 1, wherein the first solvent is shown in Table 2, respectively.

Quantum dot dispersion	(A) quantum dots	(B) the first solvent							(D) dispersant
		B-1	B-2	B-3	B-4	B-5	B-6	B-7	D-1	D-2	D-3	D-4
Preparation Example 1	30	70	-	-	-	-	-	-	-	-	-	-
Preparation Example 2	30	-	70	-	-	-	-	-	-	-	-	-
Preparation Example 3	30	-	-	70			-	-	-	-	-	-
Preparation Example 4	30	-	-	-	70		-	-	-	-	-	-
Preparation Example 5	30	-	-	-	-	70	-	-	-	-	-	-
Preparation Example 6	30	65	-	-	-	-	-	-	5	-	-	-
Preparation Example 7	30	65	-	-	-	-	-	-	-	5	-	-
Preparation Example 8	30	65	-	-	-	-	-	-	-	-	5	-
Preparation Example 9	30	65	-	-	-	-	-	-	-	-	-	5
Preparation Example 10	30	-	-	-	-	-	70	-	-	-	-	-
Preparation Example 11	30	-	-	-	-	-	65	-	5	-	-	-
Preparation Example 12	30	-	-	-	-	-	65	-	-	-	-	5
Preparation Example 13	30	-	-	-	-	-	-	65	5	-	-	-
A: Quantum dot according to Preparation Example 1 D-1: Disperbyk-111 (manufactured by BICKEM Co., Ltd., phosphate ester dispersant) Vicchemy, urethane dispersant) D-4: Disperbyk-2001 (Vicchemy, acrylic dispersant)

Primary solvent	Dielectric constant (ε) @ 20 ℃
B-1: Dipropylene glycol dimethyl ether	10.5
B-2: Dipropylene Glycol Methyl Ether Acetate	8.3
B-3: Hexyl acetate	4.42
B-4: diethyl carbonate	2.82
B-5: 2,6-dimethyl-4-heptanone	9.91
B-6: propylene glycol methyl ether (PGME)	12.3
B-7: DAA (Diacetone Alcohol)	18.2

Example  And Comparative example  : Self-luminescence  Preparation of Photosensitive Resin Composition

To prepare a self-luminous photosensitive resin composition according to Examples and Comparative Examples to the composition according to Table 3.

		Example									Comparative example
		One	2	3	4	5	6	7	8	9	One	2	3	4
Quantum Dot Dispersion (A ')	Preparation Example 1	40	-	-	-	-	-	-	-	-	-	-	-	-
	Preparation Example 2	-	40	-	-	-	-	-	-	-	-	-	-	-
	Preparation Example 3	-		40	-	-	-	-	-	-	-	-	-	-
	Preparation Example 4	-	-	-	40	-	-	-	-	-	-	-	-	-
	Preparation Example 5	-	-	-	-	40	-	-	-	-	-	-	-	-
	Preparation Example 6	-	-	-	-	-	40	-	-	-	-	-	-	-
	Preparation Example 7	-	-	-	-	-	-	40	-	-	-	-	-	-
	Preparation Example 8	-	-	-	-	-	-	-	40	-	-	-	-	-
	Preparation Example 9	-	-	-	-	-	-	-	-	40	-	-	-	-
	Preparation Example 10	-	-	-	-	-	-	-	-	-	40	-	-	-
	Preparation Example 11	-	-	-	-	-	-	-	-	-	-	40	-	-
	Preparation Example 12	-	-	-	-	-	-	-	-	-	-	-	40	-
	Preparation Example 13	-	-	-	-	-	-	-	-	-	-	-	-	40
Alkali-soluble resin (B ')		20	20	20	20	20	20	20	20	20	20	20	20	20
Photopolymerizable Compound (C ')		20	20	20	20	20	20	20	20	20	20	20	20	20
Photoinitiator (D ')		5	5	5	5	5	5	5	5	5	5	5	5	5
Second solvent (E ')		15	15	15	15	15	15	15	15	15	15	15	15	15
A ': Quantum dot dispersion B' according to Preparation Example 3 'Alkali-soluble resin C' according to Preparation Example 2 C: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) D ': Irgacure-907 (BASF E ': propylene glycol monomethyl ether acetate (PGMEA)

Color filter Glass substrate Manufacturing

The color filter was manufactured using the self-luminous photosensitive resin composition prepared according to the above Examples and Comparative Examples. Specifically, each self-luminous photosensitive resin composition was applied on 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 transmissive pattern of horizontal × vertical 20 mm × 20 mm squares and a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm ² under an atmospheric atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern. The film thickness of the self-luminous color pattern prepared above was 3.0 μm.

Experimental Example

(1) Dispersion particle size measurement of quantum dot dispersion and self-luminous photosensitive resin composition

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 agglomerated, the dispersion particle size becomes large, thereby causing a problem in that the luminescence property is degraded.

(2) photoluminescence intensity measurement

Among the color filters in which the self-luminous pixels were formed, the light-converted area was measured by a 365nm-type 4W UV irradiator (VL-4LC, VILBER LOURMAT) in the pattern part formed by the pattern of 20mm × 20mm square, It measured using USB2000 + (made by Ocean Optics). As the measured photoluminescence intensity is higher, it can be determined to exhibit excellent self-luminescence characteristics, and the results of photoluminescence intensity measurement are shown in Table 4 below.

	Quantum dot dispersion particle size (nm)	Self-luminous photosensitive resin composition particle size (nm)	Photoluminescence intensity
Example 1	7	8	53,275
Example 2	8	9	55,935
Example 3	8	8	59,354
Example 4	7	7	53,215
Example 5	8	7	54,252
Example 6	7	8	58,446
Example 7	9	10	57,243
Example 8	7	8	55,658
Example 9	8	9	54,982
Comparative Example 1	15	1152	18,542
Comparative Example 2	13	921	25,654
Comparative Example 3	15	865	28,569
Comparative Example 4	35	2671	6,179

As can be seen from Table 4, it was possible to provide a quantum dot dispersion having excellent photoluminescence quantum efficiency with excellent dispersion characteristics by using a solvent having a dielectric constant of less than 12 when manufacturing the quantum dot dispersion.

Claims (9)

1. Quantum dots; And

   A dielectric constant of less than 12.0 at 20 ° C .;

   However, halogenated hydrocarbon solvents; Aromatic hydrocarbon solvents; And aliphatic saturated hydrocarbon solvents.
2. The method of claim 1,

   The first solvent is a quantum dot dispersion having a dielectric constant of less than 8.0 at 20 ℃.
3. The method of claim 2,

   The first solvent is a quantum dot dispersion having a dielectric constant of less than 6.0 at 20 ℃.
4. The method of claim 1,

   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, isopentyl butanoate, ethyl methyl carbonate, pentyl pentanoate, isoamyl propionate, isobutyl isovalerate, propyl isovalerate, 2- (2- (vinyloxy) ethoxy) propane , 1-allyloxy-2-isoproxy-ethane, (2-isobutoxy-ethoxy) -ethene, 1-vinyloxy-2-isopentoxy-ethane, 1- A quantum dot dispersion comprising one or more selected from the group consisting of vinyloxy-2-pentoxy-ethane.
5. The method of claim 1,

   The quantum dot dispersion is a quantum dot dispersion further comprises one or more selected from the group consisting of a phosphate ester dispersant, an acrylic dispersant and a urethane-based dispersant.
6. A quantum dot dispersion according to any one of claims 1 to 5; And

   Photopolymerizable compounds; Alkali-soluble resins; Photopolymerization initiator; And at least one member selected from the group consisting of a second solvent.
7. The method of claim 6,

   The quantum dot dispersion is self-luminous photosensitive resin composition which is contained in 3 to 80 parts by weight based on 100 parts by weight of the total of the self-luminous photosensitive resin composition.
8. The color filter containing the hardened | cured material of the self-luminous photosensitive resin composition of Claim 6.
9. An image display apparatus comprising the color filter according to claim 8.