JP2021043452A - Quantum dot dispersion, self-emission photosensitive resin composition comprising the same, and color filter and image display device manufactured by using the composition - Google Patents

Abstract

To provide a quantum dot dispersion and a self-emission photosensitive resin composition having excellent dispersibility and capable of achieving excellent emission characteristics while containing no components harmful for a human body.SOLUTION: The quantum dot dispersion comprises a quantum dot and a first solvent having a dielectric constant of less than 12.0 at 20°C, and further comprises at least one component selected from a group consisting of a phosphate ester-based dispersant, an acrylic dispersant and a urethane-based dispersant, however, the dispersion contains none of a halogenated hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent and an aliphatic saturated hydrocarbon-based solvent. The self-emission photosensitive resin composition comprises the above quantum dot dispersion and a second solvent having a dielectric constant of less than 8.5 at 20°C, and further contains at least one component selected from a group consisting of a photopolymerizable compound, an alkali-soluble resin and a photopolymerization initiator.SELECTED DRAWING: None

Description

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

A color filter is a thin-film film-type optical component that extracts three colors of red, green, and blue from white light and enables them in minute pixel units. The size of one pixel is tens to 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 block the boundary portion between each pixel. Usually, the pixel portions in which the three primary colors of red R, green G, and blue B) are arranged in a predetermined order are laminated in order.

Recently, as one of the methods for embodying a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied, but light emitted from a light source passes through the color filter. There is a problem that a part of the color is absorbed by the color filter and the light 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 such as various image display devices, not only excellent pattern characteristics but also high color reproduction rate and excellent high brightness and high brightness / dark ratio performance are achieved. In order to solve such a problem, a method for manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.

The 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 of chloroform, toluene, n-hexane, or benzene. It is sold dispersed in a non-polar solvent that is harmful to the human body. In the case of the above-mentioned solvent, it is a highly volatile compound (Volatile Organic Compound), or it is carcinogenic and neurotoxic, and there is a high risk of abnormal reproductive function. is required.

Korean Patent Publication No. 2015-0034013 describes a quantum dot-resin nanocomposite and a method for producing the same, and describes a quantum dot-resin nanocomposite in which a curable resin and a large number of quantum dots exist in the form of nanoparticles. It discloses related contents.

Korean Patent Publication No. 2016-0069393 relates to a matrix resin; and a quantum dispersed in the matrix resin with respect to a method for producing a light conversion composite material, a light conversion composite material, a light conversion film containing the same, a backlight unit, and a display device. It is a light conversion composite material containing 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. The contents relating to the optical conversion composite material in which the wave number q of the peak point (peak point) is 0.0056 Å ^{-1 to} 0.045 Å ^{-1 are disclosed.}

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

Therefore, there is a demand for the development of a quantum dot dispersion and a self-luminous photosensitive resin composition which are excellent in dispersibility and can realize excellent light emitting characteristics even though they do not contain components harmful to the human body.

Korean Patent Publication No. 2015-0034013 (2015.04.02.) Korean Patent Publication No. 2016-0069393 (2016.06.16.)

The present invention provides a quantum dot dispersion containing no solvent harmful to the human body, and a self-luminous photosensitive resin composition containing the same.

The present invention also provides a quantum dot dispersion having excellent dispersibility and light emitting characteristics, and a self-luminous photosensitive resin composition containing the same.

The present invention also provides a color filter and an image display device having excellent light emission characteristics, which are produced by using the above-mentioned quantum dot dispersion and self-luminous photosensitive resin composition.

The quantum dot dispersion according to the present invention for achieving the above object contains quantum dots; and a first solvent having a dielectric constant of less than 12.0 at 20 ° C.; however, a halogenated hydrocarbon solvent; aromatic hydrocarbons. It is characterized by not containing a hydrogen-based solvent; and an aliphatic saturated hydrocarbon-based solvent;

The present invention further comprises a self-luminous photosensitive resin composition further comprising one or more selected from the group consisting of the above-mentioned quantum dot dispersion; photopolymerizable compound; alkali-soluble resin; photopolymerization initiator; and second solvent. Provide things.

The present invention also provides a color filter containing a cured product of the self-luminous photosensitive resin composition described above.

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

Since the quantum dot dispersion according to the present invention and the self-luminous photosensitive resin composition containing the same include a solvent having a specific dielectric constant, there is an advantage that it is excellent in dispersibility and can realize excellent light emitting characteristics. , Has the advantage of not containing human toxic substances.

Further, the color filter and the image display device manufactured by the self-luminous photosensitive resin composition according to the present invention have an advantage that they are excellent in light emitting characteristics.

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

When any member is said to be "above" another member in the present invention, this is not only when the arbitrary member is in contact with the other member, but also between the two members yet another member. Including the case where is present.

When any part of the present invention is said to "contain" a component, this does not exclude other components, but may further include other components, unless otherwise stated. Means.

<Quantum dot dispersion>
The homogeneity of the present invention relates to quantum dot dispersions. Specifically, the homogeneity of the present invention comprises quantum dots; and a first solvent having a dielectric constant of less than 12.0 at 20 ° C.; however, halogenated hydrocarbon solvents; aromatic hydrocarbon solvents; and It 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 dots can refer to nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When such nanoparticles have semiconductor characteristics, they are called quantum dots. When the quantum dot receives energy from the outside and becomes an excited state, the quantum dot emits energy due to the energy band gap corresponding to the quantum dot itself.

The color filter produced by the self-luminous photosensitive resin composition according to the present invention can emit light (photoluminescence) by light irradiation by containing the quantum dots.

In a normal image display device including a color filter, white light passes through the color filter to realize color, but 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 produced by the self-luminous 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, and moreover. Since the light having a color is emitted, the color reproducibility is further excellent, and the light is emitted in all directions by the optical luminescence, so that the viewing angle can be improved.

The quantum dot particles that can emit light when stimulated by light are not particularly limited. For example, it is selected from the group consisting of II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; group IV elements or compounds containing them; and combinations thereof, which may be used alone or in combination of two. The above can be mixed and used.

Specifically, the group II-VI 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, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, CdHgTe, HgZnS, HgZnSe, HgZnS It is selected from, but is not limited to, a group consisting of four element compounds selected from the group consisting of CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof.

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 a mixture thereof; A three-element 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, GaAlPAs. It is selected from the group consisting of four element compounds selected from the group consisting of GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and mixtures thereof.

The IV-VI group semiconductor compound is a two-element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe and mixtures thereof; SnSeS, SnSeTe, SnSte, PbSeS, PbSeTe, PbSe, SnPbS, SnP. A three-element compound selected from the group consisting of SnPbTe and a mixture thereof; and one or more selected from the group consisting of a four-element compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe and a mixture thereof. Not limited to these.

The group IV element or a compound containing the same is not limited to these, but 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 be a homogeneous single structure; a dual structure such as a core-shell, gradient structure, or a mixed structure thereof.

Specifically, in the core-shell dual structure, the substances that make up each core and shell can consist of the aforementioned mentioned semiconductor compounds that are different from each other. For example, the core may contain, but is not limited to, one or more substances selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO. Absent. The shell may contain, but is not limited to, one or more substances selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe and HgSe.

The quantum dots may, but are not limited to, those in which a part of the surface is replaced with an organic ligand. The organic ligand is preferable because it can be bound to the surface of the quantum dots and can play a role of stabilizing the quantum dots. The organic ligand is not limited in the present invention, but is not limited to C5-C20 alkylcarboxylic acid, alkenylcarboxylic acid or alkynylcarboxylic acid; pyridine (pyridine); mercapto alcohol; thiol; phosphine ( Phosfine); phosphine oxide; primary amine; secondary amine; and the like can be included.

As a method for substituting a part of the surface of the quantum dot with an organic ligand, the usual method used in the art can be used without limitation in the present invention.

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

The wet chemical step 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 to the surface of the quantum dot crystal and acts as a dispersant to regulate the crystal growth, so that it can be used in organic metal chemical vapor deposition processes and molecular beam epitaxy. Since the growth of nanoparticles can be controlled by using a step that is easier and cheaper than such a vapor deposition method, it is preferable to produce the quantum dots according to the present invention by using the wet chemical step.

The quantum dots may be contained 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 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. If the quantum dots are contained in less than the above range, the photosensitive characteristics may be slightly deteriorated, and if the quantum dots are contained in excess of the above range, other configurations described later, such as alkali-soluble resin and photopolymerizable, may be compared with the quantum dots. Since the content of the composition such as a compound is relatively small, there is a problem that the production of a color filter may be somewhat difficult, so that it is preferably included in the above range.

The quantum dot dispersion according to the present invention contains 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;

The halogenated hydrocarbon solvent may include, but is not limited to, for example, chloroform, dichloromethane, methylene chloride carbon 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 can include, but is not limited to, chain alkanes such as N-hexane, pentane and heptane, cyclic alkanes such as cyclopentane and cyclohesisane, 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, and 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 operator can be protected from 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 that it is excellent in quantum dot dispersion characteristics by containing a first solvent satisfying the dielectric constant value. Thereby, the color filter and the image display device manufactured by the self-luminous photosensitive resin composition containing the quantum dot dispersion according to the present invention have an advantage that they are excellent in realizing the light emitting characteristics.

When the dielectric constant of the first solvent is 12.0 or more at 20 ° C., the dispersibility of the quantum dots is slightly lowered, and along with this, a phenomenon in which the quantum dots are aggregated occurs and the overall light emission characteristics are lowered. Therefore, it is preferable to use a first solvent having a dielectric constant of less than 12.0 at 20 ° C. because a color filter having non-uniform performance can be produced.

In yet 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, isopentylbutanoate, ethylmethylcarbonate, pentylpentanoate, isoamylpropionate, isobutylisovalerate, propylisovalerate, 2- (2- (vinyloxy) ethoxy) propane, 1- It may contain one or more selected from the group consisting of allyloxy-2-isopropoxy-ethane, (2-isobutoxy-ethoxy) -ethane, 1-vinyloxy-2-isopentoxy-ethane, 1-vinyloxy-2-pentoxy-ethane. it can.

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

In still another embodiment of the present invention, the quantum dot dispersion can further contain one or more selected from the group consisting of phosphate ester dispersants, acrylic dispersants and urethane dispersants.

When the quantum dot dispersion further contains one or more selected from the group consisting of the phosphoric acid ester-based dispersant, the acrylic-based dispersant, and the urethane-based dispersant, the dispersibility between the quantum dots and the first solvent is improved. It has the advantage of excellent quantum efficiency.

The phosphoric acid ester-based dispersant may contain a phosphoric acid ester-based compound, and the phosphoric acid ester-based compound may be phosphoric acid ester ((HO) ₂ PO (OR)) or phosphoric acid (H _3). It can _{include a hydroxy group existing in PO 4} ) or a form in which the hydrogen atom of the hydroxy group is substituted or unsubstituted with another functional group. For example, the phosphate ester compounds, (H 2 _PO 3 ^_-) of but may be expressed in a form, but is not limited thereto. Further, in the present invention, the "phosphoric acid ester system" may include one or more selected from the group consisting of a phosphorous acid derivative, a phosphoric acid derivative, a phosphonic acid derivative and a phosphinic acid derivative.

When the dispersant contains the phosphoric acid ester compound, there is an advantage that a decrease in light efficiency and a deterioration in photosensitive characteristics can be suppressed.

The phosphoric acid ester compound may further contain one or more of a polyether moiety, a polyester moiety and a phosphoric acid group in one molecule.

In the present invention, the "poly-" can refer to a compound consisting of a large number of repeating units, and the "polyester moiety" and the "polyester moiety" are repeating units containing an ether group or an ester group, respectively. Can be referred to as a portion consisting of 1 to 20. Preferably, in the present invention, the repeating unit can be 5 to 20, more preferably 10 to 20, which has the advantage of excellent compatibility.

When the phosphoric acid ester compound further contains a polyether moiety in one molecule, there is an advantage that compatibility with an alkali-soluble resin described later is improved, and the phosphoric acid ester compound has a polyester moiety in one molecule. When the compound is further contained, there is an advantage that the compatibility with the alkali-soluble resin and the dissolution property in the alkali developing solution are improved. When the phosphoric acid ester compound further contains a phosphoric acid group in one molecule, it can act as a protective layer through adsorption on the surface of the quantum dots, and has an advantage of deagglomerating the quantum dots.

Preferably, the phosphate ester compound according to the invention can contain a polyether moiety, a polyester moiety and a phosphate group in one molecule, in which case the quantum dots are deaggregated to reduce the dispersion particle size. It is most preferable because it has compatibility with an alkali-soluble resin and solubility properties in an alkali developing solution, and thus has an advantage of being advantageous 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 is a self-luminous photosensitive resin composition described later. Can be involved in solubility in. When the acid value of the phosphoric acid ester compound is 10 (KOHmg / g) or more, specifically 10 to 200 (KOHmg / g), from the viewpoint of the development speed of the self-luminous photosensitive resin composition containing the dispersant. preferable. If the acid value is less than the above range, it may be somewhat difficult to secure a sufficient development speed, and if it exceeds the above range, the adhesion to the substrate is reduced and a short circuit of the pattern is likely to occur. It is preferable to satisfy the above range because a problem may occur in which the storage stability of the composition is lowered and the viscosity is increased.

Examples of the acrylic dispersant include acrylic block copolymers. 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 the acid group is preferable.

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

Examples of the quantum dot adsorption block containing the quantum dot adsorption group include those configured by utilizing a monomer having an acid group together with a monomer having a basic group.

Examples of the monomer having a basic group include a monomer having a primary amino group, a secondary amino group, a tertiary amino group or a quaternary ammonium group. Specific examples of the above-mentioned compounds include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, diethylacrylamide, dimethylaminopropylmethacrylamide, and acryloylmorpholin. , Vinyl imidazole, 2-vinylpyridine, monomer having amino group and caprolactone skeleton; reaction product of compound having glycidyl group such as glycidyl (meth) acrylate and compound having one secondary amino group in the molecule. (Meta) acryloylalkyl isocyanate compound and 4- (2-aminomethyl) -pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-hydroxyethyl) pyridine, 1- (2-aminoethyl)- Examples thereof include a reaction product with piperazine, 2-amino-6-methoxybenzothiazole, 1- (2-hydroxyethylimidazole), N, N-diallyl melamine, N, N-dimethyl-1,3-propanediamine and the like.

Examples of the monomer having an acid group include a monomer 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-acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, and styrenesulfonic acid.

Examples of the block containing no 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 thereof include unsaturated carboxylic acid alkyl esters; unsaturated carboxylic acid aryl alkyl esters such as benzyl (meth) acrylate; blocks derived from 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 anionic polymerization.

The amine value of the acrylic block copolymer is usually 0 to 200 mgKOH / g, preferably 0 to 120 mgKOH / g, and 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 value 29 mgKOH / g) ”,“ Disperbyk (registered trademark) -2020 (amine value 38 mgKOH / g) ”,“ Disperbyk (registered trademark) -2050 (amine value 30 mgKOH / g) ” , "Disperbyk (registered trademark) -2070 (amine value 20 mgKOH / g)" and the like.

The urethane-based dispersant includes 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, the method described in Japanese Patent Application Laid-Open No. 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, 3,3'-dimethylbiphenyl-4,4'-diisocyanate;
Aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatemethylene) cyclohexane, and alicyclic compounds. Formula polyisocyanate;
A polyisocyanate having an isocyanul group derived from the diisocyanate (such as a polyisocyanate having an isocyanul group formed by trimerizing the diisocyanate);
Polyisocyanate obtained by reacting polyol with diisocyanate;
Polyisocyanate obtained by a burette reaction of a diisocyanate compound; and the like.

Among the polyisocyanate compounds, a polyisocyanate having an isocyanul group derived from a diisocyanate such as toluene diisocyanate and isophorone diisocyanate is preferable.

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

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 thereof include modified products of low molecular weight monools such as methanol and ethanol.

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

Examples of the polyester compound include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol and the like. Modified products of alkylene glycols;
Modified products of low molecular weight 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 methylpentandiol, 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 (aromatic polyester polyol, etc.);
Polyvalent hydroxy group compounds such as polycarbonate polyol, acrylic polyol, polytetramethylene hexaglyceryl ester (tetrahydroxymodified product of hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid. Esters with dicarboxylic acids such as;
Examples thereof include a polyhydric hydroxy group-containing compound such as monoglyceride obtained by a transesterification reaction between a polyvalent hydroxy group-containing compound such as glycerin and a fatty acid ester; and the like.

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

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 a column chromatography method.

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 a dispersant can be used.

As the basic group-containing compound, a compound having an active hydrogen atom of Zelevitinov and at least one nitrogen atom-containing basic group, for example, a polyol having an N, N-di-substituted 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) -morpholin, 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. Among them, amines having a heterocyclic nitrogen atom are preferable.

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.

Commercially available products of the urethane-based dispersant 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, manufactured by Big Chemie). (Manufactured by Big Chemie), Disperbyk-182 (amine value 13 mgKOH / g, manufactured by Big Chemie) and the like.

In the present specification, the amine value means the amine value per 1 g of the solid content of the dispersant, and a potentiometric titration method using a 0.1 mol / l hydrochloric acid aqueous solution [for example, COMITE (AUTO TITRATOR COM-900,, BURET B-900, TISTATIONK-900), manufactured by Hiranuma Sangyo Co., Ltd.], and then converted to the equivalent of potassium hydroxide.

The dispersant may be contained in an amount of 1 to 250 parts by weight, preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the solid content of the quantum dots. When the dispersant is contained within the above range, the deagglomeration effect of the quantum dots is excellent, and the precipitation phenomenon due to the difference in polarity in the quantum dot dispersion according to the present invention and the self-luminous photosensitive resin composition containing the dispersant is suppressed. This is preferable because it can act as a protective layer for quantum dots during the manufacturing process of the color filter.

<Self-luminous photosensitive resin composition>
Yet another aspect of the present invention is a self-luminous photosensitive further comprising one or more selected from the group consisting of the quantum dot dispersion described above; and a photopolymerizable compound; an alkali-soluble resin; a photopolymerization initiator; and a second solvent. Regarding the sex 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 5 to 70 parts by weight, based on 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-mentioned quantum dot dispersion within the above range, there is an advantage that a color filter having excellent light emitting characteristics can be produced. If the quantum dot dispersion is contained below the range, the emission characteristics may be slightly deteriorated, and if the quantum dot dispersion is contained beyond the range, the content of other configurations becomes relatively small. , Since the formation of the pattern can be somewhat difficult and the reliability can be lowered, it is preferable that the pattern is included in the above range.

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

The type of the monofunctional monomer is not particularly limited, and for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Can be mentioned.

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

The type of the polyfunctional monomer is not particularly limited, and is, for example, trimethylolpropanetri (meth) acrylate, ethoxylated trimethylolpropanetri (meth) acrylate, propoxylated trimethylolpropanetri (meth) acrylate, and penta. Elythritol 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 and the like can be 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 Co., Ltd.

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, based on 100 parts by weight of the solid content of the self-luminous photosensitive resin composition. Can be included in. When the photopolymerizable compound is contained within the above range, there is an advantage that it is preferable from the viewpoint of the strength and smoothness of the pixel portion.

If the photopolymerizable compound is contained in less than the above range, the strength of the pixel portion may be slightly lowered, and if the photopolymerizable compound is contained in excess of the above range, the smoothness may be slightly lowered. It is preferably included within the range.

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

The alkali-soluble resin can play a role of making the non-exposed portion of the color filter produced by the self-luminous photosensitive resin composition alkaline-soluble so that it can be removed and leaving the exposed region. Further, when the self-luminous photosensitive resin composition contains the alkali-soluble resin, the quantum dots can be uniformly dispersed in the composition, and the quantum dots are protected during the process to maintain the brightness. Can play a role.

As the alkali-soluble resin according to the present invention, one having an acid value of 50 to 200 (KOHmg / g) can be selected and used. In addition, the alkali-soluble resin can take into consideration the limitation of molecular weight and molecular weight distribution (Mw / Mn) in order to improve the 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. Directly polymerize or purchase and use so as to have the range of. An alkali-soluble resin having a molecular weight and a molecular weight distribution in the above range can improve the hardness already mentioned, and is excellent not only in high residual film ratio but also in solubility of non-exposed parts in a developing solution. The resolution can be improved.

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

At this time, the unsaturated monomer containing an unsaturated group can be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or the like. Specifically, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic acid anhydride, and citraconic acid anhydride. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl), phthalate. Examples thereof include acid mono (2-acryloyloxyethyl) and phthalate mono (2-methacryloyloxyethyl). The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxypolymer 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.

The monomers that can be copolymerized with the carboxyl group-containing unsaturated monomer include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, and 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 One selected from the group consisting of sex monomers and combinations thereof is possible.

More specifically, the copolymerizable monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxy. Styline, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, inden 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-hydroxy Propyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl 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, methoxy Diethylene 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, a. Sobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, Unsaturated carboxylic acid esters such as glycerol monoacrylate and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-amino Aminoalkyl carboxylate unsaturated carboxylates such as propyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. Ester compounds; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether Unsaturated ether compounds such as: acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide compounds such as vinylidene cyanide; acrylamide, methacrylicamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2- Unsaturated amides such as hydroxyethylmethacrylate; unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; and Polymers of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane Giant monomers having a monoacryloyl group or a monomethacryloyl group at the end of the molecular chain; non- Bulky monomers such as a monomer having a norbonyl skeleton, a monomer having an adamantan skeleton, and a monomer having a rosin skeleton that can reduce the dielectric constant value can be used.

The alkali-soluble resin is 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 solid content of the self-luminous photosensitive resin composition. Can be included.

When the alkali-soluble resin is contained in the above range, the solubility in a developing solution is sufficient, so that pattern formation is easy, film reduction of the pixel portion of the exposed portion is prevented during development, and the non-pixel portion is prevented. It is preferable because the lackability of the resin is improved. If the alkali-soluble resin is contained in the range below the above range, the non-pixel portion may be slightly missing, and if the alkali-soluble resin is contained in the range in excess of the range, the solubility in the developing solution is slightly reduced to form a pattern. Can be a little difficult.

The self-luminous photosensitive resin composition according to the present invention may contain a photopolymerization initiator, and the type of the photopolymerization initiator is particularly limited as long as it can polymerize the photopolymerizable compound. Can be used without. In particular, the photopolymerization initiator is more than an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a thioxanthone compound from the viewpoints of polymerization characteristics, start efficiency, absorption wavelength, availability, price and the like. It is preferable to use one or more compounds selected from the above group.

Specific examples of the acetphenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydride). Xyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4) -Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butane-1-one and the like can be mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 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- (fran-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 can be mentioned.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-bis). Dichlorophenyl) -4,4', 5,5'-tetraphenyl biimidazole, 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' Examples thereof include −tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5' position is replaced 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'-Tetraphenyl biimidazole, 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-phenylpropane-1-one, and commercially available products such as Irgacure OXE 01 and OXE 02 of BASF are representative. ..

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

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 solid content of the self-luminous photosensitive resin composition. . May be included in 5 parts by weight.

When the photopolymerization initiator is contained in the above range, the self-luminous photosensitive resin composition is highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained, which is preferable. Further, there is an advantage that the strength of the pixel portion formed by 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 contain a photopolymerization initiator in order to improve the sensitivity of the self-luminous photosensitive resin composition in the present invention. When the photopolymerization initiation aid is included, there is an advantage that the sensitivity is further increased and the productivity is improved.

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

As the amine compound, it is preferable to use an aromatic amine compound, specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate. Ethyl acid, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as) : Michler ketone), 4,4'-bis (diethylamino) benzophenone and the like can be used.

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

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

The photopolymerization initiation aid can be appropriately added and used as long as it does not impair the scope of the present invention.

The second solvent contained in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and may include an organic solvent usually used in the art. As the first solvent, the same solvent as the second solvent may be used, or different solvents may be used. However, the second solvent does not contain a halogenated hydrocarbon solvent; an aromatic hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent;

Specific examples of the second solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol di. 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 acetate and the like. Alkylene glycol alkyl ether acetates; 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, cyclohexanol, Alcohols such as ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone and the like can be mentioned.

The second solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. among the second solvents from the viewpoint of coatability and drying property, and more preferably alkylene glycol alkyl ether acetates, ketones, and the like. Examples thereof include esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxypropionic acid. Examples include methyl. These second solvents can be used alone or in admixture of two or more.

The second solvent may be contained 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 is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet. At times, it is preferable because the coatability can be improved. If the content of the second solvent is less than the above range, the step may become somewhat difficult as the coatability is slightly lowered, and if it exceeds the above range, the color formed by the self-luminous photosensitive resin composition. Problems can occur that can result in some degradation in filter performance.

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

The adhesion accelerator can be added to enhance the 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. Can include, but are not limited to, silane coupling agents. For example, the silane coupling agent includes trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy. Examples thereof include silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 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). -Fluorine-based surfactants such as Silicone) can be used, but the present invention is not limited to this.

In addition, the self-luminous photosensitive resin composition according to the present invention may further contain additives such as an antioxidant, an ultraviolet absorber, and an anti-aggregation agent as long as the effects of the present invention are not impaired. The agent can be appropriately added and used by those skilled in the art as long as the effect of the present invention is 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. Can be used in, but is not limited to these.

<Color filter>
Yet another aspect of the present invention relates to a color filter produced by using the self-luminous photosensitive resin composition described above.

The color filter according to the present invention contains 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; aromatics such as benzene or toluene. Light emission by containing a cured product of a self-luminous photosensitive resin composition containing a quantum dot dispersion having excellent dispersibility, which does not contain a hydrocarbon solvent; and an aliphatic saturated hydrocarbon solvent such as N-hexane; It has the advantage of being excellent in embodying the characteristics, and has the advantage of being excellent in terms of the environment because it does not contain a solvent harmful to the human body in the quantum dot dispersion.

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

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

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

A color filter including a substrate and a pattern layer as described above may further include, but is not limited to, a partition wall formed between each pattern and may further include a black matrix.

Further, a protective film formed on the upper part of the pattern layer of the color filter may be further included.

In yet another embodiment of the invention, the color filter can 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 containing red quantum dots, a green pattern layer containing green quantum dots, and a blue pattern layer containing blue quantum dots according to the present invention. it can. The red pattern layer, the green pattern layer, and the blue pattern layer can emit red light, green light, and blue light, respectively, when irradiated with light. At this time, the emitted light of the light source is not particularly limited. A light source that emits blue light can be used in terms of better color reproducibility.

The color filter may include, but is not limited to, only two color pattern layers of the red pattern layer, the green pattern layer, and the blue pattern layer. However, when the color filter includes only two kinds of color pattern layers, the pattern layer can 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 types of colors, a light source that emits light having a wavelength indicating a color other than the two types 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 which case the red quantum dots are red light and the green quantum dots are green. It emits light, and the transparent pattern layer can become blue as the blue light from the light source is transmitted as it is.

<Image display device>
Further, another aspect of the present invention relates to an image display device including the above-mentioned color filter.

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

Since the image display device according to the present invention contains a cured product of a self-luminous photosensitive resin composition containing a quantum dot dispersion having excellent dispersibility, it has an advantage of being excellent in light emitting characteristics.

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

Hereinafter, in order to specifically explain this specification, it will be described in detail by way of examples. However, the examples according to this specification can be transformed into various other forms, and it is not understood that the scope of the present specification is limited to the examples detailed below. The examples herein are provided to provide a more complete description of the specification to those with average knowledge in the art. In addition, "%" and "part" indicating the content below are based on weight unless otherwise specified.

Production Example 1: Synthesis of InP / ZnS core-shell quantum dot particles
Production 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 are placed in a reactor and evacuated. It was heated down at 120 ° C. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating at 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 rapidly cooled to room temperature, and the precipitate obtained by centrifugation was dispersed in toluene. The obtained InP semiconductor nanocrystals exhibit a maximum UV absorption wavelength of 560 to 590 nm.

Production of InP / ZnS core-shell quantum dots 2.4 mmoL of zinc acetate (0.448 g), 4.8 mmol of oleic acid and 20 mL of trioctylamine were placed in a reactor and heated under vacuum at 120 ° C. After 1 hour, the atmosphere in the reactor was converted to nitrogen and the temperature of the reactor was raised to 280 ° C. After 2 ml of the previously synthesized InP core solution was added, then 4.8 mmol of S / TOP was added, the final mixture was allowed to proceed 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 light emission spectrum of the obtained nano quantum dots was 635 nm.

Production Example 2: A flask equipped with a synthetic stirrer for an alkali-soluble resin, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube is prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, and a bird. 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 is stirred and mixed to prepare a monomer dropping funnel. After preparation, 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 of the chain transfer agent. Then, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and chain transfer agent were started to be dropped from the dropping funnel. The dropping was carried out for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature was raised to 110 ° C. and maintained for 3 hours, and then a gas introduction pipe was introduced to oxygen / nitrogen = 5/95 (v). / V) Bubbling of the mixed gas was started. Next, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were put into the flask, and 8 parts by weight at 110 ° C. The reaction for a time was continued, and then, while cooling to room temperature, 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 was obtained.

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

Examples and Comparative Examples: Production of Self-luminous Photosensitive Resin Composition The self-luminous photosensitive resin composition according to Examples and Comparative Examples was produced with the composition shown in Table 3 below.

Production of Color Filter (Glass Substrate) A color filter was produced using the self-luminous photosensitive resin composition produced in 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 quadrangular transmission pattern of width × length 20 mm × 20 mm and a line / space pattern of 1 μm to 100 μm is placed on the thin film, and ultraviolet rays are emitted with a distance of 100 μm from the test photomask. Irradiated. At this time, the ultraviolet light source is a special optical filter that uses an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio, Inc. to irradiate light in an atmospheric atmosphere with an exposure amount (365 nm) of ^{200 mJ / cm 2.} Did not use. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development. The glass plate on which the thin film was applied 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 produced above was 3.0 μm.

Experimental Example (1) Measurement of dispersion particle size of quantum dot dispersion and self-luminous photosensitive resin composition After measuring the dispersion particle size using ELSZ-2000ZS (manufactured by Otsuka Co., Ltd.), it is shown in Table 4 below. Usually, when the quantum dot particles are aggregated, the dispersed particle size becomes large, which can cause a problem that the light emitting characteristics are deteriorated.

(2) Measurement of photoluminescence intensity (photoluminescence intensity) A 365 nm type 4W UV irradiator (VL-4LC, VILBER) on a pattern portion formed by a 20 mm × 20 mm regular square pattern among color filters on which self-luminous pixels are formed. The photoconverted region was measured using LOURMAT), and the photoconverted emission intensity was measured using Specrummeter USB2000 + (manufactured by Ocean Optics). It can be judged that the higher the measured photoluminescence intensity (photoluminescence intensity), the better the self-luminous characteristic is 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 very excellent dispersion characteristics by using a solvent having a dielectric constant of less than 12 during the production of the quantum dot dispersion. Was able to be provided.

Claims (7)

Includes quantum dots; and a first solvent with a dielectric constant of less than 12.0 at 20 ° C.
Further comprising one or more selected from the group consisting of phosphoric acid ester-based dispersants, acrylic-based dispersants and urethane-based dispersants.
However, a quantum dot dispersion containing no halogenated hydrocarbon solvent; aromatic hydrocarbon solvent; and aliphatic saturated hydrocarbon solvent; and a second solvent having a dielectric constant of less than 8.5 at 20 ° C. Including
A self-luminous photosensitive resin composition further comprising one or more selected from the group consisting of a photopolymerizable compound; an alkali-soluble resin; and a photopolymerization initiator. The self-luminous photosensitive resin composition according to claim 1, wherein the first solvent has a dielectric constant of less than 8.0 at 20 ° C. The self-luminous photosensitive resin composition 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. Etheracetate, ethylo-formate, ethylbutyrate, diethylacetal, methylhexanoate, methyloctanoate, ethylisovalerate, methyl3-methylbutanoate, isopentyl3-methylbutanoate, isopentylbutanoate Ate, ethylmethyl carbonate, pentylpentanoate, isoamylpropionate, isobutylisovalerate, propylisovalerate, 2- (2- (vinyloxy) ethoxy) propane, 1-allyloxy-2-isopropoxy-ethane, ( The self-luminous photosensitive according to claim 1, which comprises one or more selected from the group consisting of 2-isobutoxy-ethoxy) -ethane, 1-vinyloxy-2-isopentoxy-ethane, and 1-vinyloxy-2-pentoxy-ethane. Resin composition. The self-luminous photosensitive resin composition according to claim 1, wherein the quantum dot dispersion is contained in an amount of 3 to 80 parts by weight based on 100 parts by weight of the entire self-luminous photosensitive resin composition. A color filter containing a cured product of the self-luminous photosensitive resin composition according to claim 1. An image display device including the color filter according to claim 6.