KR20190108366A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising: (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) quantum dots; (E) a thiol group containing compound containing a mono-thiol compound and a di-thiol compound; and (F) a solvent, wherein the mono-thiol compound is contained in a smaller amount than the di-thiol compound, to a photosensitive resin film produced using the photosensitive resin composition, and to a color filter comprising the photosensitive resin film.

Description

Photosensitive resin composition, photosensitive resin film and color filter using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

This base material relates to the photosensitive resin composition containing a quantum dot, the photosensitive resin film manufactured using the said photosensitive resin composition, and the color filter containing the said photosensitive resin film.

In general, a color filter applied to a display forms a desired pattern through an exposure process using a photomask using a photosensitive resist composition, and forms a color filter through a patterning process in which a non-exposed part is dissolved and removed through a developing process. The color filter material is alkali-soluble and requires high sensitivity, adhesion to the substrate, chemical resistance, heat resistance, and the like. However, since the curing reaction is not sufficient due to the exposure process alone, a step of thermal curing for a predetermined time at a high temperature of 200 ° C. or more is required in order to obtain required properties. Therefore, there is a limit to applications requiring low temperature processes such as electronic paper and OLED.

Meanwhile, in order to develop a photosensitive resin composition for color filters requiring relatively low temperature process such as electronic paper and OLED, efforts have been made to compensate for insufficient curing properties by adding additional compounds such as epoxide and peroxide in the composition. Not enough, there is a problem of low reliability.

The above problem is a phenomenon caused by color materials such as pigments or dyes competitively absorbing the photopolymerization initiator and the light energy, and it is difficult to obtain sufficient initiation efficiency because of the action of removing the radicals generated by the pigments and dyes, and therefore, The curing rate of the synthetic monomer is to be reduced than when the color material is not used.

Therefore, efforts are being made to develop a photosensitive resin composition which can significantly improve the reliability of chemical resistance, heat resistance and the like by using other materials instead of conventional color materials such as dyes or pigments.

One embodiment is to provide a quantum dot-containing photosensitive resin composition excellent in storage stability at refrigeration and room temperature conditions.

Another embodiment is to provide a photosensitive resin film prepared using the photosensitive resin composition.

Another embodiment is to provide a color filter including the photosensitive resin film.

Photosensitive resin composition according to one embodiment is (A) binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) quantum dots; (E) Thiol group containing compound containing a mono-thiol compound and a di-thiol compound; And (F) a solvent, wherein the mono-thiol compound is included in a smaller amount than the di-thiol compound.

The mono-thiol compound may be included in an amount of 1% by weight to 15% by weight based on the total amount of solids constituting the photosensitive resin composition.

The di-thiol compound may be included in an amount of 3 wt% to 25 wt% in the total amount of solids constituting the photosensitive resin composition.

The mono-thiol compound may include one or more of compounds represented by the following Chemical Formulas 1 and 2.

[Formula 1]

[Formula 2]

In Chemical Formula 1 and Chemical Formula 2,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 To C20 aryl group.

In Formula 1 and Formula 2, R ¹ may be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group, and R ² may be a substituted or unsubstituted C6 to C20 aryl group.

The mono-thiol compound may include one or more of compounds represented by the following Chemical Formulas 1-1 to 1-4 and Chemical Formula 2-1.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-4, n is an integer of 1 to 10.

[Formula 2-1]

The di-thiol compound may include a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

L ³ to L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The quantum dot may have a maximum fluorescence emission wavelength at 500nm to 680nm.

The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone or combinations thereof.

The binder resin may include an acrylic binder resin, a cardo binder resin, or a combination thereof.

The photosensitive resin composition may further include a diffusing agent.

The diffusing agent may be included in an amount of 0.1 wt% to 20 wt% with respect to the total amount of the photosensitive resin composition.

The diffusion agent may include barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.

The binder resin is contained in 1% by weight to 30% by weight relative to the total amount of the photosensitive resin composition, the photopolymerizable monomer is included in 0.1% to 30% by weight based on the total amount of the photosensitive resin composition, the photopolymerization initiator is 0.1 wt% to 10 wt% based on the total amount of the photosensitive resin composition, and the quantum dots may be included in an amount of 1 wt% to 40 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Polymerization inhibitors; Or a combination thereof.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition.

Another embodiment provides a color filter including the photosensitive resin film.

Other details of aspects of the invention are included in the following detailed description.

It is possible to provide a quantum dot-containing photosensitive resin composition excellent in storage stability even under refrigeration and room temperature conditions.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" refers to a C2 to C20 alkenyl group, and "cycloalkenyl group" means a C3 to C20 cycloalkenyl group. , "Heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" Means C1 to C20 alkylene group, "arylene group" means C6 to C20 arylene group, "alkyl arylene group" means C6 to C20 alkylarylene group, and "heteroarylene group" means C3 to C20 hetero It means an arylene group and a "alkoxy group" means a C1-C20 alkoxylene group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, It means substituted with a substituent of a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group or a combination thereof.

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom of N, O, S, and P is included in a chemical formula.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

Unless otherwise stated herein, "combination" means mixed or copolymerized.

Unless otherwise defined in the chemical formulas herein, when a chemical bond is not drawn at a position where a chemical bond is to be drawn, it means that a hydrogen atom is bonded at the position.

In the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Chemical Formulas 4-1 to 4-11 is included in the backbone of the resin.

Also, unless stated otherwise in the present specification, "*" means a part connected with the same or different atoms or formulas.

Photosensitive resin composition according to one embodiment is (A) binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) quantum dots; (E) Thiol group containing compound containing a mono-thiol compound and a di-thiol compound; And (F) a solvent, wherein the mono-thiol compound is included in a smaller amount than the di-thiol compound.

The quantum dot-containing photosensitive resin composition may contain a thiol group-containing compound for the purpose of improving the heat resistance to the thermal step and improving the dispersibility of the quantum dot. The thiol group-containing compound mainly uses a di-thiol compound such as ethylene glycol bis (3-mercaptopropionate). The di-thiol compound added in the composition undergoes a thiol-ene reaction with the acrylic monomer and the acrylic binder in the composition to proceed the curing reaction, ultimately forming a monolayer. The di-thiol compound has two thiol groups at both ends thereof to form a reticular network when reacted with an acryl site. In addition, since it is possible to cap the unsafe surface of the quantum dot well, it is possible to minimize the decrease in quantum efficiency due to the thermal process, it is advantageous in terms of light retention.

The ligand of the quantum dot currently synthesized is oleate, which caps the dangling bond on the surface of the quantum dot and gives dispersibility to the solvent. When the oleate ligand reacts with the di-thiol compound, the pattern profile such as CD (critical dimension, width of exposure pattern) and BP (breaking point, development time) at the initial stage of the reaction varies with storage time. . The storage stability of such fragile quantum dot-containing photosensitive resin composition has been a major obstacle to mass production of quantum dot-containing products. For example, at present, the initial CD of the quantum dot-containing photosensitive resin composition is about 112 μm, but gradually increases with storage time to about 120 μm within 12 weeks (during refrigeration).

However, according to one embodiment, by adding a small amount of mono-dendate ligand, that is, mono-thiol compound having better binding affinity with the quantum dot surface than the di-thiol compound, blocking binding to the quantum dot surface of the di-thiol compound It can dramatically improve the refrigeration and storage stability at room temperature.

Each component is demonstrated concretely below.

(E) Thiol group containing compound

The composition according to the embodiment includes a thiol group-containing compound, and the thiol group-containing compound includes a mono-thiol compound and a di-thiol compound. In addition, the mono-thiol compound is included in a smaller amount than the di-thiol compound.

When only the di-thiol compound is used as the thiol group-containing compound, the di-thiol compound and the oleate ligand on the surface of the quantum dot react to form a complex, and then exposure is performed, wherein the di-thiol compound is free. Since the reactivity of the complexed di-thiol compound is much higher than that of the thiol-ene compound, the thiol-ene reaction proceeds very rapidly, resulting in a CD change with the storage time of the composition, which ultimately results in storage of the quantum dot-containing photosensitive resin composition. This will adversely affect stability.

The thiol-ene reaction proceeds as a radical mechanism or Michael-Addition Reaction depending on the reaction conditions. If the thiol-ene reaction occurs in a complex formed by reacting a di-thiol compound with an oleate ligand on the surface of a quantum dot, If by mechanism, a polymerization inhibitor can be used to control the thiol-ene reaction rate. Therefore, the present inventors split and apply the amount of methylhydroquinone as a polymerization inhibitor to the conventional quantum dot-containing photosensitive resin composition composition (including binder resin, quantum dot, photopolymerizable monomer, photopolymerization initiator and solvent), and only the absolute CD value is different. It was confirmed that the CD increase rate with time was the same. Since the slope of the CD rise for each methylhydroquinone content is the same, the thiol-ene reaction rate causing the CD rise according to the storage time becomes a zeroth-order reaction to the concentration of methylhydroquinone, thus the thiol It was found that the reaction was not due to a radical mechanism.

That is, in order to solve the problem of deterioration in storage stability of the quantum dot-containing photosensitive resin composition (CD increase problem), complex formation between the quantum dot and the di-thiol compound and the Michael addition reaction mechanism must be blocked accordingly. (The causal relationship between the storage stability of the quantum dot-containing photosensitive resin composition and the Michael addition reaction due to the complex between the quantum dot and the di-thiol compound increases as the quantum dot content increases or the size of the quantum dot decreases even with the same quantum dot content. Evidence can also be found in the larger number of quantum dot particles), i.e., the larger the quantum dot surface area, the worse the storage stability (accelerating the rate of CD growth).

In one embodiment, in order to prevent a slow ligand exchange reaction between the quantum dot-oleate and the di-thiol compound over time, a small amount of a mono-thiol compound having better binding affinity than the di-thiol compound is added so that the mono-thiol compound is Instead of the di-thiol compound, the reaction occurs on the surface of the quantum dot and binds, and because only one thiol group is used, even if the Michael addition reaction proceeds, no crosslinking network is produced and the reaction is terminated.

Furthermore, when the mono-thiol compound is used alone or in a larger amount than the di-thiol compound, the mono-thiol compound is easily separated from the complex between the quantum dot and the mono-thiol compound and reacted with the binder again. , The molecular weight of the binder resin functioning as a binder can be made low, and ultimately, the film strength of the formed resin film can be reduced. Therefore, in one embodiment, the mono-thiol compound is used in combination with the di-thiol compound, but the content is less than the di-thiol compound.

For example, the mono-thiol compound may be included in an amount of 1 wt% to 15 wt%, such as 1 wt% to 5 wt%, based on the total amount of solids constituting the photosensitive resin composition. When the mono-thiol compound is included in less than 1% by weight based on the total amount of solids constituting the photosensitive resin composition, the effect of adding the mono-thiol compound is insignificant, and the mono-thiol compound is included in the total amount of solids constituting the photosensitive resin composition. If included in excess of 15% by weight may cause a decrease in film strength.

For example, the di-thiol compound may be included in 3% by weight to 25% by weight, such as 5% by weight to 20% by weight, based on the total amount of solids constituting the photosensitive resin composition.

For example, the mono-thiol compound may include one or more of the compounds represented by Formula 1 and Formula 2.

[Formula 1]

[Formula 2]

In Chemical Formula 1 and Chemical Formula 2,

L ¹ and L ² are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group,

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 To C20 aryl group.

For example, the mono-thiol compound may be represented by Chemical Formula 1.

For example, in Formula 1, R ¹ may be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group, and in Formula 2, R ² may be a substituted or unsubstituted C6 to C20 aryl group. .

For example, the mono-thiol compound may include one or more of compounds represented by the following Chemical Formulas 1-1 to 1-9 and Chemical Formula 2-1.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-4, n is an integer of 1 to 10.

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 2-1]

For example, the mono-thiol compound may include one or more of the compounds represented by the following Chemical Formulas 1-10 to 1-15.

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

For example, the di-thiol compound may include a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

L ³ to L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

For example, the di-thiol compound may include, but is not necessarily limited to, glycol di-3-mercaptopropionate.

(D) quantum dots

The quantum dot may have a core-shell structure, and the shell may include Zn, and a thiol group of the thiol group-containing compound may be bonded to Zn of the shell.

For example, the quantum dot absorbs light in a wavelength region of 360 nm to 780 nm, such as 400 nm to 780 nm, and emits fluorescence in a wavelength region of 500 nm to 700 nm, such as 500 nm to 580 nm, or emits fluorescence at 600 nm to 680 nm. Can be. That is, the quantum dot may have a maximum fluorescence λ _em at 500 nm to 680 nm.

The quantum dots may each independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, such as 20 nm to 50 nm. When the quantum dot has the half width of the above range, the higher the color purity, the higher the color reproducibility when used as a color material in the color filter.

Each of the quantum dots may be independently an organic material or an inorganic material or a hybrid (mixture) of an organic material and an inorganic material.

Each of the quantum dots may be independently composed of a core and a shell surrounding the core, and the core and the shell may each independently include a core, a core / shell, a core / first shell / composed of group II-IV, group III-V, or the like. It may have a structure such as a second shell, an alloy, an alloy / shell, but is not limited thereto.

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs, and alloys thereof. However, the present invention is not limited thereto. The shell surrounding the core may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, HgSe, and alloys thereof, but is not necessarily limited thereto.

In one embodiment, due to the recent increase in environmental concerns around the world and the strengthening of regulations on toxic substances, instead of light emitting materials having a cadmium-based core, the quantum yield is rather low but environmentally friendly Although a non-cadmium-based light emitting material (InP / ZnS, InP / ZeSe / ZnS, etc.) was used, it is not necessarily limited thereto.

In the case of the quantum dot of the core / shell structure, the size (average particle diameter) of each of the entire quantum dots including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

For example, the quantum dots may independently include red quantum dots, green quantum dots, or a combination thereof. The red quantum dots may each independently have an average particle diameter of 10nm to 15nm. The green quantum dots may each independently have an average particle diameter of 5nm to 8nm.

On the other hand, for dispersion stability of the quantum dot, the photosensitive resin composition according to one embodiment may further include a dispersant. The dispersant helps to uniformly disperse the light conversion material, such as quantum dots in the photosensitive resin composition, it is possible to use both nonionic, anionic or cationic dispersant. Specifically, polyalkylene glycol or esters thereof, polyoxy alkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide An adduct, alkyl amine, etc. can be used, These can be used individually or in mixture of 2 or more types. The dispersant may be used in an amount of 0.1 wt% to 100 wt%, such as 10 wt% to 20 wt%, based on the solid content of the light conversion material such as quantum dots.

The quantum dot may be included 1 wt% to 40 wt%, such as 3 wt% to 30 wt% based on solids based on the total amount of the photosensitive resin composition. When the surface-modified quantum dot is included in the above range, the light conversion rate is excellent and may have excellent processability without inhibiting pattern characteristics and developing characteristics.

(A) binder resin

The binder resin may include an acrylic binder resin, a cardo binder resin, or a combination thereof.

The acrylic binder resin is a copolymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the acrylic binder resin include polybenzyl methacrylate, (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these alone or in combination thereof. You may mix and use the above.

The weight average molecular weight of the acrylic binder resin may be 5,000 g / mol to 15,000 g / mol. 　 When the weight average molecular weight of the said acrylic binder resin is in the said range, it is excellent in adhesiveness with a board | substrate, good physical and chemical properties, and a viscosity is suitable.

The acid value of the acrylic binder resin may be 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cardo-based binder resin may include a repeating unit represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxy alkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁷ R ¹⁸ , SiR ¹⁹ R ²⁰ , wherein R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, or Any one of the linking groups represented by Formulas 4-1 to 4-11,

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Chemical Formula 4-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ or a phenyl group.)

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid anhydride residue,

t1 and t2 are each independently an integer of 0-4.

The weight average molecular weight of the cardo-based binder resin may be 500 g / mol to 50,000 g / mol, such as 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, the pattern formation is well performed without residue during the preparation of the photosensitive organic layer, and there is no loss of the film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may include a functional group represented by Formula 5 at at least one of both terminals.

[Formula 5]

In Chemical Formula 5,

Z ³ may be represented by the following Chemical Formulas 5-1 to 5-7.

[Formula 5-1]

(In Formula 5-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group.)

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

(In Formula 5-5, R ^d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group or C2 to C20 alkenylamine group.)

[Formula 5-6]

[Formula 5-7]

The cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis (4-oxyranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetra carboxylic dianhydride, benzophenone tetra carboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetra carboxylic dianhydride, phen Anhydride compounds such as relenetetracarboxylic acid dianhydride, tetrahydrofurantetracarboxylic acid dianhydride and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Solvent compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

When the binder resin is a cardo-based binder resin, the developability of the photosensitive resin composition including the same is excellent, and the sensitivity is excellent at the time of photocuring.

The binder resin may include a thiol group.

The binder resin may be included in an amount of 1 wt% to 30 wt%, such as 3 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(B) photopolymerizable monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei cultivating the T (weeks)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 0.1 wt% to 30 wt%, such as 1 wt% to 20 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the above range, curing occurs during exposure in the pattern forming process, thereby providing excellent reliability, and excellent heat resistance, light resistance, chemical resistance, resolution, and adhesion of the pattern.

(C) photopolymerization initiator

As the photopolymerization initiator, an initiator commonly used in the photosensitive resin composition, for example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound or the like can be used. .

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt -Butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4' -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine , 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4 -Bis (trichloromethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

Examples of the oxime compound include O-acyl oxime compound, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyl oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one and the like Can be used. Specific examples of the O-acyl oxime compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane- 1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butane-1-one oxime- And O-acetates.

In addition to the above compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, a fluorene compound, or the like.

The photopolymerization initiator may be used together with a photosensitizer which causes a chemical reaction by absorbing light and transferring energy after being excited.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and the like. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, such as 0.1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, it is excellent in the sensitivity and developability balance during exposure to obtain a pattern having excellent resolution without a residual film.

(F) solvent

When the photosensitive resin composition contains photoconversion materials such as quantum dots instead of pigments or dyes as color materials, polarities such as solvents used in general photosensitive resin compositions such as propylene glycol monomethyl ether acetate, ethanol, ethylene diglycol methyl ethyl ether, etc. It is difficult to use a solvent. However, as described above, according to one embodiment, the quantum dot surface is modified with a compound having one thiol group at one end and an alkoxy group, a cycloalkyl group, a carboxyl group, or a hydroxyl group at one end thereof. The quantum dots can be used even in a polar solvent, and the problem of lowering the light conversion rate of the quantum dots can also be solved.

That is, the photosensitive resin composition according to one embodiment may be an alcohol such as methanol or ethanol as a solvent; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propylether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like may be used, but is not limited thereto.

For example, the solvent may be a glycol ether such as ethylene glycol monoethyl ether or ethylene diglycol methylethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxy ethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propylether acetate; It is preferable to use alcohols, such as ethanol, or a combination thereof.

For example, the solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrroli Polar solvents, including dine, N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone, or a combination thereof.

The solvent may be included in the balance based on the total amount of the photosensitive resin composition, for example, 20 wt% to 80 wt%, such as 35 wt% to 80 wt%. When the solvent is included in the above range, as the photosensitive resin composition has an appropriate viscosity, it may have excellent coating properties in large area coating using spin coating and slits.

(G) diffuser (or diffuser dispersion)

The photosensitive resin composition according to one embodiment may further include a diffusing agent.

For example, the diffusion agent may include barium sulfate (BaSO ₄ ), calcium carbonate (CaCO ₃ ), titanium dioxide (TiO ₂ ), zirconia (ZrO ₂ ), or a combination thereof.

The diffusing agent reflects light that is not absorbed by the above-described photoconversion material and allows the photoconversion material to absorb the reflected light again. That is, the diffusion agent may increase the amount of light absorbed by the light conversion material, thereby increasing the light conversion efficiency of the photosensitive resin composition.

The diffusion agent may have an average particle diameter (D ₅₀ ) of 150nm to 250nm, specifically 180nm to 230nm. When the average particle diameter of the diffusing agent is in the above range, it may have a more excellent light diffusion effect, it is possible to increase the light conversion efficiency.

The diffusing agent may be included in an amount of 0.1 wt% to 20 wt%, such as 1 wt% to 15 wt%, based on the total amount of the photosensitive resin composition. When the diffusing agent is included in less than 0.1% by weight relative to the total amount of the photosensitive resin composition, it is difficult to expect the effect of improving the light conversion efficiency by using the diffusing agent, and when included in excess of 20% by weight, the pattern characteristics may be reduced. There is concern

(H) other additives

The photosensitive resin composition according to an embodiment may further include a polymerization inhibitor including a hydroquinone compound, a catechol compound, or a combination thereof. As the photosensitive resin composition according to an embodiment further includes the hydroquinone compound, the catechol compound, or a combination thereof, after printing (coating) the photosensitive resin composition, normal temperature crosslinking may be prevented during exposure.

For example, the hydroquinone compound, the catechol compound or a combination thereof may be hydroquinone, methyl hydroquinone, methoxyhydroquinone, t-butyl hydroquinone, 2,5-di- t -butyl hydroquinone, 2,5- Bis (1,1-dimethylbutyl) hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, catechol, t-butyl catechol, 4-methoxyphenol, fatigue Roll, 2,6-di- t -butyl-4-methylphenol, 2-naphthol, tris (N-hydroxy-N-nitrosophenylaminato-O, O ') aluminum (Tris (N-hydroxy-N -nitrosophenylaminato-O, O ') aluminium) or a combination thereof, but is not necessarily limited thereto.

The hydroquinone-based compound, catechol-based compound or a combination thereof may be used in the form of a dispersion, the polymerization inhibitor in the form of the dispersion is 0.001% to 1% by weight, such as 0.01% to 0.1% by weight relative to the total amount of the photosensitive resin composition May be included as a%. When the stabilizer is included in the above range, it is possible to solve the problem over time at room temperature, and at the same time prevent the degradation of the sensitivity and the surface peeling phenomenon.

In addition, the photosensitive resin composition according to the embodiment is, for improving heat resistance and reliability, malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Or a combination thereof.

For example, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, etc. in order to improve adhesion to a substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ-glycol. Propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like at the time of reading. These may be used alone or in combination of two or more thereof.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, it is excellent in adhesion, storage property and the like.

In addition, the photosensitive resin composition may further include a surfactant, for example, a fluorine-based surfactant, in order to improve coating properties and prevent defects, that is, to improve leveling performance, as necessary.

The fluorine-based surfactant may have a low weight average molecular weight of 4,000 g / mol to 10,000 g / mol, specifically, may have a weight average molecular weight of 6,000 g / mol to 10,000 g / mol. In addition, the fluorine-based surfactant may have a surface tension of 18 mN / m to 23 mN / m (measured in 0.1% propylene glycol monomethyl ether acetate (PGMEA) solution). If the weight average molecular weight and the surface tension of the fluorine-based surfactant is within the above range can further improve the leveling performance, prevent the occurrence of stains during high speed coating (high speed coating), because there is less foaming due to less bubbles It gives excellent properties to slit coating, which is a high speed coating method.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like from BM Chemie Co .; Mecha packs F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Grass Co., Ltd .; Toray silicone (Note)社SH-28PA ^{®, ®} -190 copper, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ® , and the like; Fluorine-type surfactants commercially available under the names F-482, F-484, F-478, F-554, etc. of DIC Corporation can be used.

In addition, the surfactant may be a silicone-based surfactant in addition to the above-described fluorine-based surfactant. Specific examples of the silicone-based surfactants include, but are not limited to, TSF400, TSF401, TSF410, TSF4440, etc. of Toshiba Silicon Corporation.

The surfactant may be included in an amount of 0.01 parts by weight to 5 parts by weight, such as 0.1 parts by weight to 2 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, foreign matters are less generated after development.

In addition, the photosensitive resin composition according to the embodiment may further be added a certain amount of other additives such as antioxidants within a range that does not impair the physical properties.

Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition described above.

Another embodiment provides a color filter including the photosensitive resin film. The manufacturing method of the color filter is as follows.

(1) application and coating film forming step

The above-mentioned photosensitive resin composition is subjected to a desired thickness, for example, 2 μm to 10 μm, using a method such as spin or slit coating method, roll coating method, screen printing method, applicator method, etc. on a substrate subjected to a predetermined pretreatment. After coating, the coating is formed by heating at a temperature of 70 ° C to 90 ° C for 1 to 10 minutes to remove the solvent.

(2) exposure step

In order to form the pattern required for the obtained coating film, a predetermined form of mask is interposed, and then active rays such as UV rays of 190 nm to 450 nm, for example, 200 nm to 500 nm are irradiated. As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and X-rays, an electron beam, etc. can also be used in some cases.

Although an exposure amount changes with the kind, compounding quantity, and dry film thickness of each component of the said photosensitive resin composition, it is 500 mJ / cm <^2> or less (by 365 nm sensor), for example when using a high pressure mercury lamp.

(3) developing stage

Subsequent to the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form an image pattern. That is, when developing with alkaline developing solution, a non-exposed part will melt | dissolve and an image color filter pattern will be formed.

(4) post-processing steps

The image pattern obtained by the above development can be cured by heating again or by actinic radiation irradiation in order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability and the like.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

(Quantum solution dispersion solution)

Preparation Example 1

12.102 g of InP / ZeSe / ZnS-oleate ligand quantum dot solution (fluorescence λ _em = 532 nm, FWHM = 37 nm, Green QD, Hansol Chemical) (23.04% solids) and binder resin (TB04, Tacoma) dispersed in cyclohexyl acetate (CHA)社) (solid content 49.4%) To 1.959 g of the compound represented by the following formula 1-1 0.2g, 0.8g of the compound represented by the formula 3-1 was added and stirred at room temperature (20 ℃) for 12 hours solids 26.36% A quantum dot dispersion solution of was prepared.

[Formula 1-1]

[Formula 3-1]

Preparation Example 2

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by the following formula 1-2 was used instead of the compound represented by the formula 1-1.

[Formula 1-2]

Preparation Example 3

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by the following formula 1-3 was used instead of the compound represented by the formula 1-1.

[Formula 1-3]

Preparation Example 4

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula 1-4 was used instead of the compound represented by Chemical Formula 1-1.

[Formula 1-4]

(In Formula 1-4, n is an integer of 3)

Preparation Example 5

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by Formula 2-1 was used instead of the compound represented by Formula 1-1.

[Formula 2-1]

Comparative Production Example 1

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula 3-1 was not used.

Comparative Production Example 2

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that the compound represented by Chemical Formula 1-1 was not used.

Comparative Production Example 3

A quantum dot dispersion solution was prepared in the same manner as in Preparation Example 1, except that 0.8 g of the compound represented by Chemical Formula 1-1 was used and 0.2 g of the compound represented by Chemical Formula 3-1 was used.

(Photosensitive resin composition production)

Using the components mentioned below, the photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1 below.

Specifically, after dissolving the photopolymerization initiator in the solvent, it was sufficiently stirred at room temperature for 2 hours. Subsequently, binder resin (Tacoma, 49.4% of solid content) and the quantum dot dispersion solution were added together in the preparation example, followed by stirring at room temperature for 2 hours. After adding a diffusing agent and a leveling agent thereto, the mixture was stirred at room temperature for 1 hour, and the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition. (The content of the dispersant is 15% by weight based on the quantum dot solid content.)

Binder resin

Acrylic Binder Resin (TB04, Tacoma)

Photopolymerizable monomer

tricyclodecane dimethanol diacrylate (TCI)

Photopolymerization initiator

PBG 305 (tronly)

Quantum dots

(Q-1) Quantum dot dispersion solution of Preparation Example 1

(Q-2) Quantum dot dispersion solution of Preparation Example 2

(Q-3) Quantum dot dispersion solution of Preparation Example 3

(Q-4) Quantum dot dispersion solution of Preparation Example 4

(Q-5) Quantum dot dispersion solution of Preparation Example 5

(Q-6) Quantum dot dispersion solution of Comparative Preparation Example 1

(Q-7) Quantum dot dispersion solution of Comparative Preparation Example 2

(Q-8) Quantum dot dispersion solution of Comparative Preparation Example 3

menstruum

Propylene Glycol Monomethyl Ether Acetate (PGMEA, Sigma-Aldrich)

Diffuser

Titanium dioxide dispersion (TiO ₂ solids 20 wt%, average particle size: 200nm, Dito Technology Co., Ltd.)

Other additives

Leveling Agent (F-554, DIC Corporation)

(Unit: weight% of total solution) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Binder resin 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 Photopolymerizable monomer 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Photopolymerization initiator 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Quantum dots (Q-1) 17.4 - - - - - - - (Q-2) - 17.4 - - - - - - (Q-3) - - 17.4 - - - - - (Q-4) - - - 17.4 - - - - (Q-5) - - - - 17.4 - - - (Q-6) - - - - - 17.4 - - (Q-7) - - - - - - 17.4 - (Q-8) - - - - - - - 17.4 menstruum 57 57 57 57 57 57 57 57 Diffuser 12 12 12 12 12 12 12 12 Other additives 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5

Evaluation 1: Evaluation of light conversion rate and light retention rate

The photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3, respectively, were coated on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150, 150rpm) to a thickness of 5 μm. Thereafter, pre-baking (PRB) was performed at 100 ° C. for 1 minute using a hot-plate, and the initial blue light conversion was measured.

Exposure machine (Ushio社, ghi broadband) was irradiated with UV to the output (power) of 60 mJ / cm ² to 100mJ / cm ² using a, a post for 30 minutes in the convection clean oven (jongro Co., Ltd.) to 180 ℃ under nitrogen atmosphere Post-baking (POB) was performed and the blue light conversion was measured.

For the pre-baking step and the post-baking step, the light conversion rate and process retention of blue light incident from the BLU to green were evaluated, and the results are shown in Table 2 below. The blue light conversion rate was measured using a CAS 140 CT spectrometer, a bare glass was placed on a blue BLU (455 nm) covered with a diffusing film, measured with a detector, and the reference was first obtained, followed by Examples 1 to 5 and A single film coated with the photosensitive resin compositions according to Comparative Examples 1 to 3 was placed thereon, and an increase amount of a peak converted to green relative to a decrease amount of a blue light absorption peak was calculated to measure a light conversion ratio (Green / Blue). In addition, how long the light conversion rate in the initial PRB step is maintained in the POB step, that is, the light retention rate during the process from the PRB step to the POB step was also measured.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Light conversion rate (%) 23 24 24 23 22 23 22 23 Mineral retention rate (%) 96 95 95 95 94 94 94 94

Evaluation 2: storage stability evaluation

After storing the photosensitive resin composition prepared in Examples 1 to 5 and Comparative Examples 1 to 3 at refrigerated (4 ℃) and room temperature (25 ℃), respectively, the developing time (BP) breaking point and viscosity Measured.

(BP evaluation)

The photosensitive resin composition was coated on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150, 150rpm) to a thickness of 5 μm, and then pre-cured at 100 ° C. for 1 minute using a hot-plate. baking (pre-baking; PRB) of, and the exposure system to (Ushio社, ghi broadband) 60 mJ / cm 2 to, TAMAH aqueous solution of 0.05% concentration was irradiated with UV to the output (power) of 100mJ / cm ² using a In the process of developing, using a spray type developer, the time (time) at which the pattern starts to be seen during development was measured and the results are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 cold storage Early 35 35 34 36 35 34 33 35 1 week 34 34 33 37 35 35 35 38 2 weeks 34 35 34 36 36 36 36 38 3 weeks 35 35 35 36 37 38 37 39 4 Weeks 36 34 33 37 37 38 37 40 5 Weeks 36 35 35 36 37 39 37 41 6 Weeks 35 36 34 37 38 40 39 43 Week 7 36 35 34 36 38 42 40 44 8 Weeks 35 34 35 37 39 43 42 46 Room temperature Early 35 35 34 36 35 34 33 35 12 hours 34 35 34 36 35 35 35 36 24 hours 35 35 34 36 36 36 36 38 36 hours 35 36 35 37 36 38 38 40 48 hours 36 36 35 37 37 40 38 42 60 hours 37 36 35 38 37 43 40 42 72 hours 37 37 36 38 40 44 43 44

(Viscosity evaluation)

The photosensitive resin composition was measured using a Brookfield III viscometer (# 40 spindle, 50 rpm) 1 minute after loading, and the average value of the results of five repeated measurements is shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 cold storage Early 4.9 5.0 4.9 5.1 5.0 4.9 5.0 4.9 1 week 4.8 5.1 4.9 5.1 5.1 5.0 5.2 5.0 2 weeks 4.9 5.0 4.8 5.0 5.1 5.1 5.2 5.2 3 weeks 4.9 5.0 4.9 5.0 5.1 5.2 5.3 5.3 4 Weeks 4.9 5.0 4.9 5.1 5.1 5.2 5.3 5.5 5 Weeks 4.9 5.0 4.9 5.1 5.2 5.2 5.5 5.5 6 Weeks 4.9 5.0 4.9 5.1 5.2 5.3 5.5 5.6 Week 7 4.9 5.0 4.9 5.0 5.2 5.4 5.6 5.7 8 Weeks 4.9 5.0 4.9 5.1 5.2 5.5 5.6 5.8 Room temperature Early 4.9 5.0 4.9 5.1 5.0 4.9 5.0 4.9 12 hours 4.9 5.0 4.9 5.1 5.1 5.0 5.1 5.0 24 hours 4.9 5.0 4.9 5.1 5.0 5.0 5.2 5.1 36 hours 5.0 5.1 5.0 5.2 5.1 5.1 5.4 5.3 48 hours 5.0 5.1 5.0 5.2 5.1 5.3 5.5 5.5 60 hours 5.0 5.2 4.9 5.2 5.2 5.5 5.7 5.6 72 hours 5.0 5.1 4.9 5.2 5.2 5.6 5.8 5.7

As shown in Table 2 to Table 4, the photosensitive resin composition according to Examples 1 to 5 has the same level of optical properties and storage stability at the same time, compared to the photosensitive resin composition according to Comparative Examples 1 to 3 This can be confirmed to be excellent.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (17)

(A) binder resin;
(B) photopolymerizable monomers;
(C) photoinitiator;
(D) quantum dots;
(E) Thiol group containing compound containing a mono-thiol compound and a di-thiol compound; And
(F) comprises a solvent,
The mono-thiol compound is a photosensitive resin composition containing less than the di-thiol compound.
The method of claim 1,
The mono-thiol compound is a photosensitive resin composition containing 1 to 15% by weight based on the total amount of solids constituting the photosensitive resin composition.
The method of claim 2,
The di-thiol compound is a photosensitive resin composition containing 3% by weight to 25% by weight in the total solids constituting the photosensitive resin composition.
The method of claim 1,
The mono-thiol compound is a photosensitive resin composition comprising at least one of the compounds represented by the following formula (1) and (2):
[Formula 1]

[Formula 2]

In Chemical Formula 1 and Chemical Formula 2,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 To C20 aryl group.
The method of claim 4, wherein
R ¹ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C1 to C20 alkoxy group,
R ² is a substituted or unsubstituted C 6 to C 20 aryl group.
The method of claim 1,
The mono-thiol compound is a photosensitive resin composition comprising at least one of the compounds represented by the following formula 1-1 to formula 1-4 and formula (2-1).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-4, n is an integer of 1 to 10.
[Formula 2-1]

The method of claim 1,
The di-thiol compound is a photosensitive resin composition comprising a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
L ³ to L ⁵ are each independently a substituted or unsubstituted C1 to C20 alkylene group.
The method of claim 1,
The quantum dot is a photosensitive resin composition having a maximum fluorescent light emission wavelength at 500nm to 680nm.
The method of claim 1,
The solvent is propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, ethanol, ethylene glycol dimethyl ether, ethylene diglycol methyl ethyl ether, diethylene glycol dimethyl ether, 2-butoxyethanol, N-methylpyrrolidine, A photosensitive resin composition comprising N-ethylpyrrolidine, propylene carbonate, γ-butyrolactone or a combination thereof.
The method of claim 1,
The binder resin is a photosensitive resin composition comprising an acrylic binder resin, a cardo binder resin or a combination thereof.
The method of claim 1,
The photosensitive resin composition further comprises a diffusing agent.
The method of claim 11,
The diffusing agent is 0.1 to 20% by weight based on the total amount of the photosensitive resin composition.
The method of claim 11,
The diffusion agent is a photosensitive resin composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.
The method of claim 1,
The binder resin is contained in 1% by weight to 30% by weight relative to the total amount of the photosensitive resin composition, the photopolymerizable monomer is included in 0.1% to 30% by weight based on the total amount of the photosensitive resin composition, the photopolymerization initiator is 0.1 wt% to 10 wt% with respect to the total amount of the photosensitive resin composition, and the quantum dot is included in 1 wt% to 40 wt% with respect to the total amount of the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine-based surfactants; Polymerization inhibitors; Or a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-15.
A color filter comprising the photosensitive resin film of claim 16.