KR102471746B1 - Photosensitive resin composition, photosensitive resin layer using same and color filter - Google Patents

Abstract

(A) quantum dots; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E-1) a first solvent; and (E-2) a second solvent different from the first solvent, wherein the second solvent is cyclohexyl acetate, and the second solvent is present in an amount of 40% to 80% by weight based on the total amount of the first solvent and the second solvent. A photosensitive resin composition included in weight percent, a photosensitive resin film prepared using the same, and a color filter including the photosensitive resin film are provided.

Description

Photosensitive resin composition, photosensitive resin film and color filter using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film prepared using the same, and a color filter including the photosensitive resin film.

In general, a color filter applied to a display forms a color filter through a patterning process in which a desired pattern is formed through an exposure process in which a photomask is applied using a photosensitive resist composition, and an unexposed portion is dissolved and removed through a development process. Materials for color filters are alkali soluble and require high sensitivity, adhesion to substrates, chemical resistance, and heat resistance. However, in general, since the curing reaction is not sufficient only by the exposure process, a step of thermally curing at a high temperature of 200 ° C. or more for a certain period of time is required to obtain the required properties. Therefore, there is a limit to applications that require low-temperature processes such as electronic paper and OLED.

On the other hand, in order to develop a photosensitive resin composition for color filters that requires a relatively low-temperature process application such as electronic paper and OLED, efforts have been made to supplement insufficient curing characteristics by adding additional compounds, such as epoxides and peroxides, to the composition, but the curing degree is poor. There is a problem that reliability is low because it is not sufficient.

The above problem is a phenomenon that occurs because color materials such as pigments or dyes competitively absorb light energy with photopolymerization initiators, and since pigments and dyes act to remove generated radicals, it is difficult to obtain sufficient initiation efficiency. The curing rate of the synthetic monomer is reduced compared to the case where no color material is used.

Therefore, efforts are being made to develop a photosensitive resin composition capable of remarkably improving reliability such as chemical resistance and heat resistance 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 that has excellent patternability and can maintain excellent optical properties of quantum dots even after a thermal process.

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.

One embodiment is (A) quantum dots; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E-1) a first solvent; and (E-2) a second solvent different from the first solvent, wherein the second solvent is cyclohexyl acetate, and the second solvent is present in an amount of 40% to 80% by weight based on the total amount of the first solvent and the second solvent. It provides a photosensitive resin composition included in weight%.

The first solvent may be a compound having a lower boiling point than the second solvent.

The binder resin may include a cardo-based binder resin including a structural unit represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

R ¹¹ and R ¹² are each independently represented by Formula 2 below;

[Formula 2]

In Formula 2,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group;

L ² is an oxygen atom or a sulfur atom;

R ¹ is "a C1 to C10 alkyl group substituted with a C1 to C10 alkylthio group" or "a C6 to C20 aryl group substituted with a C1 to C10 alkylthio 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 (where R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following Any one of the linking groups represented by Formula 1-1 to Formula 1-11;

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In Chemical Formula 1-5,

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 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

Z ² is an acid anhydride residue;

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

The cardo-based binder resin may have a weight average molecular weight of 2,000 g/mol to 20,000 g/mol.

The binder resin may further include at least one binder resin selected from the group consisting of an acrylic binder resin and an epoxy binder resin.

The photosensitive resin composition may further include 0.5 wt% to 10 wt% of (F) a diffusing agent based on the total amount of the photosensitive resin composition.

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

The photosensitive resin composition may further include a thiol-based additive.

The thiol-based additive may include at least two or more functional groups represented by the following Chemical Formula 7 at the terminal.

[Formula 7]

In Formula 7,

L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 arylene group. It is a C2 to C20 heteroarylene group.

The quantum dots may be quantum dots that absorb light of 360 nm to 780 nm and emit fluorescence at 500 nm to 700 nm.

The photosensitive resin composition may include, based on the total amount of the photosensitive resin composition, 1% to 50% by weight of (A) quantum dots; 1% to 20% by weight of the (B) binder resin; 1% to 10% by weight of the (C) photopolymerizable monomer; 0.01% to 5% by weight of the (D) photopolymerization initiator; and (E) the remainder of the solvent.

The photosensitive resin composition may include a polymerization inhibitor; malonic acid; 3-amino-1,2-propanediol; silane-based coupling agents; leveling agent; fluorine-based surfactants; or a combination thereof.

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

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

The specific details of other aspects of the present invention are included in the detailed description below.

Even after the color filter manufacturing process including the heat process, it is possible to provide a photosensitive resin composition having excellent patternability while minimizing degradation of optical properties of quantum dots.

1 is a focused ion beam (FIM) scanning electron microscope (SEM) photograph (X20000) of a cross-section of a pattern of a photosensitive resin film prepared using the photosensitive resin composition according to Example 1.
2 is a focused ion beam (FIM) scanning electron microscope (SEM) photograph (X20000) of a cross-section of a pattern of a photosensitive resin film prepared using the photosensitive resin composition according to Comparative Example 1.
3 is a focused ion beam (FIM) scanning electron microscope (SEM) photograph (X20000) of the patterned surface of the photosensitive resin film prepared using the photosensitive resin composition according to Example 1.
4 is a focused ion beam (FIM) scanning electron microscope (SEM) photograph (X20000) of the patterned surface of the photosensitive resin film prepared using the photosensitive resin composition according to Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined 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" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group, and , "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 a C1 to C20 alkylene group, "arylene group" means a C6 to C20 arylene group, "alkylarylene group" means a C6 to C20 alkylarylene group, and "heteroarylene group" means a C3 to C20 hetero It means an arylene group, and "alkoxyylene group" means a C1 to C20 alkoxyylene group.

Unless otherwise specified herein, "substitution" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, an amine group, an imino group, Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, ether group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, 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, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a substituent of a combination thereof.

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

In addition, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid". "That means both are possible.

In this specification, unless otherwise specified, "combination" means mixing or copolymerization.

Unless otherwise defined in the chemical formula within this specification, if 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 to the position.

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

In addition, unless otherwise specified in this specification, "*" means a portion connected to the same or different atoms or chemical formulas.

The photosensitive resin composition according to one embodiment includes (A) quantum dots; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; (E-1) a first solvent; and (E-2) a second solvent different from the first solvent, wherein the second solvent is cyclohexyl acetate, and the second solvent is present in an amount of 40% to 80% by weight based on the total amount of the first solvent and the second solvent. included in weight percent.

In general, photosensitive resin compositions are composed of pigments or dyes, photopolymerizable monomers, binder resins, photopolymerization initiators, solvents, additives, etc., but the photosensitive resin composition according to an embodiment uses quantum dots to impart color characteristics instead of pigments or dyes. include Since the color filter manufactured using the photosensitive resin composition according to the embodiment emits light by itself, the color reproduction rate is improved compared to the color filter manufactured using the conventional photosensitive resin composition, especially the lateral luminance is increased, and the wide viewing angle is improved. There are advantages to having.

Quantum dots are surrounded by organic ligands having non-polar hydrocarbon chain end groups on the particle surface from the synthesis stage or post-processing, and thanks to the ligands, they can be dispersed in hydrophobic organic solvents, and quantum dots Since the surface can be well passivated to maintain photostability, it can be used in various applications. Commonly used ligands include oleic acid, stearic acid, myristic acid, trioctyl phosphine, trioctyl amine, and dodecane thiol.

Well-known solvents capable of dispersing quantum dots include hexane, cyclohexane, toluene, chloroform, etc. In particular, toluene, which has a relatively high boiling point, maintains the quantum efficiency of quantum dots, and is easy to store, has been mainly used. However, since the solvents are classified as harmful substances or regulated substances, there is a problem in that they are not suitable as solvents for a color filter process in which a complex continuous process is performed. In particular, highly volatile solvents such as hexane and chloroform are classified as carcinogens.

On the other hand, in the case of chloroform, it is uniquely excellent in compatibility with both quantum dots and components other than quantum dots (binder resin, photopolymerizable monomer, photopolymerization initiator, thiol-based additives, extenders, other additives, etc.), making it a solvent for quantum dot-containing compositions. However, stability cannot be guaranteed due to its low boiling point, and bubbles can be formed on the surface or inside during pattern formation, so it cannot be a fundamental solution.

In addition, a dispersant (an organic monomolecular or polymer binder having an amine group, a thiol group, a carboxyl acid group, etc.) is used to forcibly disperse the quantum dots in a polar solvent used as a solvent for conventional photosensitive resin compositions, but the quantum dots The optical properties and quantum efficiency stability of the quantum dots cannot be guaranteed according to the increase in the content of the dispersant used to improve the dispersibility, and finally becomes a factor that inhibits the pattern characteristics of the photosensitive resin composition containing quantum dots.

However, according to one embodiment, it is possible to simultaneously dissolve the quantum dot inorganic particles and organic components other than the quantum dots (binder resin, photopolymerizable monomer, photopolymerization initiator, thiol-based additive, extender, other additives, etc.), even compared to chloroform. Dispersion stability and pattern of the photosensitive resin composition containing quantum dots by using cyclohexyl acetate, an amphoteric solvent having both a polar group and a non-polar group, in a specific content range that can stably maintain the optical properties of the photosensitive resin composition containing quantum dots. Fairness and light characteristics (light conversion rate) can be effectively maintained.

Specifically, by using the amphoteric solvent cyclohexyl acetate in the content range of 40% to 80% by weight relative to the total amount of the total solvent instead of conventional chloroform, quantum dots that may occur after the quantum dot-containing photosensitive resin composition undergoes a thermal process It can solve the problem of deterioration of the optical properties of the film, the problem of pinholes on the pattern surface and the undercut of the pattern cross section that occur during the pattern process.

Each component is specifically described below.

(E) solvent

The second solvent, cyclohexyl acetate, is used together with a different first solvent, but the amount thereof is 40% to 80% by weight based on the total amount of the first solvent and the second solvent, so that the quantum dots after the thermal process It is possible to greatly improve pattern properties while minimizing deterioration in optical properties.

The cyclohexyl acetate is an amphoteric compound, and is used together with a compound having a lower boiling point than the cyclohexyl acetate, and when the content thereof is 40% to 80% by weight based on the total amount of the solvent, the quantum dot containing the solvent is contained. The photosensitive resin composition not only does not greatly deteriorate the optical properties of the quantum dots even after a thermal process, but at the same time can greatly improve the pattern properties of the photosensitive resin film prepared using the composition. And, these properties are compared to other amphoteric compounds other than cyclohexyl acetate, such as pentyl acetate, hexyl acetate, decyl acetate, dodecyl acetate, isoamyl acetate, diethyl ether, dibutyl ether, methyl isobutyl ketone, etc. It corresponds to a unique effect that only cyclohexyl acetate has. (In other words, if a compound other than cyclohexyl acetate is used as the amphoteric compound, the effect of preventing deterioration of optical properties and improving pattern properties after the thermal process cannot be realized at the same time.)

For example, the first solvent may be a compound having a lower boiling point than the second solvent, such as propylene glycol (mono) methyl ether acetate (PGMEA). (Cyclohexyl acetate has a boiling point of 172 ° C, propylene glycol (mono) methyl ether acetate has a boiling point of 145 ° C)

For example, the photosensitive resin composition according to one embodiment uses a mixed solvent of cyclohexyl acetate and propylene glycol (mono) methyl ether acetate as a solvent, and the cyclohexyl acetate is 40% to 80% by weight based on the total amount of the mixed solvent. When included as, it is possible to maximize the effect of securing optical properties and improving pattern properties of quantum dots after thermal processing.

The solvent may be included in a balance amount, for example, 30 wt% to 80 wt%, for example, 30 wt% to 70 wt%, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity and thus the photosensitive resin film manufacturing processability is excellent.

(A) quantum dots

The quantum dots may absorb light in a wavelength range of 360 nm to 780 nm, for example, 400 nm to 780 nm, and emit fluorescence in a wavelength range of 500 nm to 700 nm, for example, 500 nm to 580 nm, or emit fluorescence in a wavelength range of 600 nm to 680 nm. . That is, the light conversion material may have a maximum fluorescence emission wavelength (fluorescence λ _em ) at 500 nm to 680 nm.

Each of the quantum dots may independently have a full width at half maximum (FWHM) of 20 nm to 100 nm, for example, 20 nm to 50 nm. When the quantum dots have a full width at half maximum in the above range, the color reproduction rate is increased when used as a color material in a color filter according to high color purity.

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

The quantum dots may each independently consist of a core and a shell surrounding the core, and the core and shell may each independently consist of a core, a core/shell, a core/first shell/ It may have a structure of a second shell, alloy, alloy/shell, etc., 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. , but is not necessarily 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, since interest in the environment has greatly increased worldwide in recent years and regulations on toxic substances have been strengthened, instead of light emitting materials having a cadmium-based core, the quantum yield is rather low, but environmentally friendly A non-cadmium-based light emitting material (InP/ZnS) was used, but is not necessarily limited thereto.

The structure of the quantum dots is not particularly limited, but in the case of the quantum dots having a core/shell structure, the size (average particle diameter) of each quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 15 nm.

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

Meanwhile, for dispersion stability of the quantum dots, the photosensitive resin composition according to an 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, and all of nonionic, anionic or cationic dispersants may be used. Specifically, polyalkylene glycol or esters thereof, polyoxyalkylene, 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 Adducts, alkyl amines, and the like may be used, and these may be used alone or in combination of two or more. The dispersant may be used in an amount of 0.1 wt % to 100 wt %, for example, 10 wt % to 20 wt %, based on the solid content of light conversion materials such as quantum dots.

The quantum dots may be included in an amount of 1 wt% to 50 wt%, for example, 10 wt% to 50 wt%, based on the total amount of the photosensitive resin composition according to one embodiment. When the quantum dots are included within the above range, the light conversion rate is excellent, and pattern characteristics and development characteristics are not impaired, so that excellent fairness may be obtained.

(B) binder resin

The binder resin may include a cardo-based binder resin including a structural unit represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

R ¹¹ and R ¹² are each independently represented by Formula 2 below;

[Formula 2]

In Formula 2,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group;

L ² is an oxygen atom or a sulfur atom;

R ¹ is "a C1 to C10 alkyl group substituted with a C1 to C10 alkylthio group" or "a C6 to C20 aryl group substituted with a C1 to C10 alkylthio 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 (where R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following Any one of the linking groups represented by Formula 1-1 to Formula 1-11;

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In Chemical Formula 1-5,

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 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

Z ² is an acid anhydride residue;

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

Specifically, in Formula 2, an oxygen atom or a sulfur atom (more specifically, a sulfur atom) of L ² and a sulfur atom constituting a thio group of R ¹ act as ligands on the surface of the quantum dots and bind or passivate the quantum dots. , the dispersion and stability of the quantum dots are improved, and ultimately the deterioration of the light conversion rate can be prevented.

Quantum dots, which play a key role in converting blue light, have hydrophobicity because they are surrounded by a hydrophobic ligand, and because of this, a problem of poor dispersibility inevitably occurs when the quantum dots are added to a hydrophilic photosensitive resin composition. In order to solve this dispersibility problem, many studies on passivation including ligand substitution on the surface of quantum dots are being conducted. . However, since the ligand-exchanged quantum dots (surface-modified quantum dots) in this way are greatly reduced in light conversion ability by the thermal process during the patterning process of the photosensitive resin composition, surface modification of the quantum dots alone is not enough to completely solve the conventional problems. was

However, according to one embodiment, a cardo-based binder in order to further improve the dispersibility of quantum dots and the efficiency of light conversion by heat without significantly deteriorating the light conversion ability of quantum dots by thermal process by not using a separate ligand exchange material. By introducing thiol and/or sulfide (-SH and/or -S-) into the resin, the cardo-based binder resin directly acts as a ligand on the surface of the quantum dots and binds them or passivates the quantum dots, thereby reducing the number of quantum dots. It has a positive effect on dispersion and stability. Furthermore, by additionally using an acrylic binder resin or an epoxy binder resin together with the cardo-based binder resin, the entire composition is maintained in a stable state even after the thermal process, so that the effect of homogenizing morphology characteristics including light conversion efficiency of quantum dots That is, it is possible to minimize the formation of holes in the surface of the resin film and minimize dark spots in the single film of the resin film.

For example, R ¹ may be a C1 to C5 alkyl group substituted with a C1 to C5 alkylthio group or a C6 to C10 aryl group substituted with a C1 to C5 alkylthio group. When R ¹ is not an alkylthio group, but an alkyl group or an aryl group substituted with an epoxy group or an acrylate group, the patternability after development is greatly reduced, and both storage stability and photoconversion retention after thermal processing are greatly reduced, which is not preferable.

For example, Z ² may be represented by any one selected from the group consisting of Formulas 3 to 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

In Formula 3,

L ³ is a single bond, an oxygen atom, a sulfur atom, *-C(=O)-* or *-CR ² R ³ -* (R ² and R ³ are each independently a halogen atom-substituted or unsubstituted C1 to C10 alkyl group).

For example, in Chemical Formula 3, L ³ may be a sulfur atom.

The cardo-based binder resin may include two or more structural units represented by Chemical Formula 1.

The cardo-based binder resin may have a weight average molecular weight of 2,000 g/mol to 20,000 g/mol, for example, 3,000 g/mol to 10,000 g/mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, patterns are well formed without residue during manufacturing of color filters, there is no loss of film thickness during development, and good patterns can be obtained.

The cardo-based binder resin may include a functional group represented by Chemical Formula 10 at at least one of both terminals.

[Formula 10]

In Formula 10,

Z ³ may be represented by Formulas 10-1 to 10-7 below.

[Formula 10-1]

(In Formula 10-1, 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 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

(In Formula 10-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Formula 10-6]

[Formula 10-7]

The photosensitive resin composition according to one embodiment may further include an acrylic binder resin.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof 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 %, for example, 10 wt % to 40 wt %, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, or vinylbenzylmethyl ether; 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 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; and the like, and these may be used alone or in combination of two 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, etc. may be mentioned, but are not limited thereto, and these may be used alone or in combination of two. The above can also be used in combination.

The acrylic binder resin may have a weight average molecular weight of 5,000 g/mol to 20,000 g/mol.　When the weight average molecular weight of the acrylic binder resin is within the above range, adhesion to the substrate is excellent, physical and chemical properties are good, and the viscosity is appropriate.

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 pixel pattern resolution is excellent.

The acrylic binder resin may have a double bond equivalent of 150 g/mol to 400 g/mol. When the double bond equivalent of the acrylic binder resin is within the above range, it is possible to effectively prevent a decrease in light absorption after a thermal process.

The photosensitive resin composition according to one embodiment may further include an epoxy-based binder resin.

For example, the pre-oxygenated binder resin may include a novolak type epoxy compound, a bisphenol A type epoxy compound, a cresol novolak type epoxy compound, a biphenyl type epoxy compound, and the like, but is not necessarily limited thereto.

The epoxy-based binder resin may have an epoxy equivalent of 100 g/eq to 190 g/eq. When an epoxy-based binder resin having an epoxy equivalent in the above range is used, it can be of great help in improving pattern properties and minimizing a decrease in light conversion retention after a thermal process.

For example, the epoxy-based binder resin may be represented by Formula 6 below.

[Formula 6]

In Formula 6,

R ⁴ is a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group;

n1 to n3 are each independently an integer of 1 to 20;

For example, in Chemical Formula 6, n1 to n3 may each independently be an integer of 1 to 13, and n1+n2+n3 may be an integer of 15.

The 'cardo-based binder resin' may be included in a greater content than 'at least one or more binder resins selected from the group consisting of acrylic-based binder resins and epoxy-based binder resins'. For example, when the cardo-based binder resin is included in an amount greater than that of the acrylic-based binder resin or the epoxy-based binder resin, effects such as prevention of deterioration of light absorption rate and light conversion rate after a thermal process can be achieved simultaneously with excellent pattern properties.

The binder resin may be included in an amount of 1 wt % to 20 wt %, for example, 5 wt % to 15 wt %, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent sensitivity, developability, resolution, and linearity of the pattern may be obtained.

(C) photopolymerizable monomer

As the photopolymerizable monomer, a monofunctional or multifunctional 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, sufficient polymerization occurs during exposure in the pattern formation process, thereby forming a pattern having excellent heat resistance, light resistance and chemical resistance.

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, and 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 Acrylates, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, trimethylol propane tri( meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of monofunctional esters of (meth)acrylic acid include Aronix M- ^101® , M- ^111® , and M- ^114® from Toagosei Chemical Industry Co., Ltd.; KAYARAD TC-110S ^® of Nippon Kayaku Co., Ltd., the same TC-120S ^® , etc.; Osaka Yuki Kagaku Kogyo Co., Ltd.'s V- ^158® , V- ^2311® , etc. are mentioned. Examples of the bifunctional ester of (meth)acrylic acid include Aronix M- ^210® , M- ^240® , and M- ^6200® of Toagosei Chemical Industry Co., Ltd.; KAYARAD HDDA ^® from Nippon Kayaku Co., Ltd., HX-220 ^® , R-604 ^® , etc.; Examples include V- ^260® , V- ^312® , and V-335 ^HP® of 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® , and M from Toagosei Chemical Industry Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^® , etc.; KAYARAD TMPTA ^® from Nippon Kayaku Co., Ltd., Copper DPCA-20 ^® , Copper-30 ^® , Copper-60 ^® , Copper-120 ^® , etc.; V-295 ^® , Dong-300 ^® , Dong-360 ^® , Dong-GPT ^{® , Dong-3PA ® ,} Dong-400 ^® and the like of Osaka Yuki Kayaku Kogyo Co., Ltd. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used after being treated with an acid anhydride to impart better developability.

The photopolymerizable monomer may be included in an amount of 1 wt % to 10 wt %, for example, 1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, sufficient curing occurs during exposure in the pattern forming process, resulting in excellent reliability, and excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern.

(D) photopolymerization initiator

The photopolymerization initiator is an initiator generally used in a photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, an amino ketone-based compound etc. can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, p-t-butyltrichloro acetophenone, p-t-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 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-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4 '-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

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

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyldimethylketal.

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, etc. are mentioned. .

Examples of the oxime-based compound include O-acyloxime-based compounds, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used. Specific examples of the O-acyloxime 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)-octan-1-one oxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime- O-acetate 　 etc. are mentioned.

An example of the amino ketone compound is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1), etc.

As the photopolymerization initiator, a carbazole-based compound, a diketone compound, a sulfonium borate-based compound, a diazo-based compound, an imidazole-based compound, or a biimidazole-based compound may be used in addition to the above compounds.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and then transferring the energy thereto.

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 heard

The photopolymerization initiator may be included in an amount of 0.01 wt % to 5 wt %, for example, 0.1 wt % to 1 wt %, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, excellent reliability can be obtained due to sufficient curing during exposure in the pattern forming process, excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern, and a decrease in transmittance due to the unreacted initiator. can prevent

(F) Diffusion agent

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

For example, the diffusing 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 light conversion material, and allows the light conversion material to absorb the reflected light again. That is, the diffusion agent may increase the light conversion efficiency of the photosensitive resin composition by increasing the amount of light absorbed by the light conversion material.

The diffusing agent may have an average particle diameter (D ₅₀ ) of 150 nm to 250 nm, specifically 180 nm to 230 nm. When the average particle diameter of the diffusing agent is within the above range, a superior light diffusion effect may be obtained and light conversion efficiency may be increased.

The diffusing agent, specifically, the solid content of the diffusing agent may be included in an amount of 0.1 wt % to 10 wt %, for example, 0.5 wt % to 8 wt %, based on the total amount of the photosensitive resin composition. When the diffusing agent is included in an amount of less than 0.5% by weight based on the total amount of the photosensitive resin composition, it is difficult to expect an effect of improving light conversion efficiency by using the diffusing agent, and when the diffusing agent is included in an amount exceeding 10% by weight, the pattern characteristics of the color filter are included. This decreases, and light conversion efficiency may also decrease.

(G) other additives

To improve the stability and dispersibility of the quantum dots, the photosensitive resin composition according to an embodiment may further include a thiol-based additive.

The thiol-based additive may be substituted on the shell surface of the quantum dots to improve dispersion stability of the quantum dots in a solvent, thereby stabilizing the quantum dots.

The thiol-based additive may have 2 to 10, for example, 2 to 4 thiol groups (-SH) at the terminal depending on its structure.

For example, the thiol-based additive may include at least two or more functional groups represented by the following Chemical Formula 7 at the terminal.

[Formula 7]

In Formula 7,

L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 arylene group. It is a C2 to C20 heteroarylene group.

For example, the thiol-based additive may be represented by Formula 8 below.

[Formula 8]

In Formula 8,

L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 arylene group. It is a C2 to C20 heteroarylene group,

u1 and u2 are each independently an integer of 0 or 1.

For example, in Chemical Formulas 7 and 8, L ¹ and L ² may each independently be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

Specific examples of the thiol-based additive include pentaerythritol tetrakis (3-mercaptopropionate) represented by Formula 8a, trimethylolpropane tris (3-mercaptopropionate) represented by Formula 8b below -Mercaptopropionate) (trimethylolpropane tris (3-mercaptopropionate)), pentaerythritol tetrakis (mercaptoacetate) represented by the following formula 8c, trimethylolpropane tris represented by the following formula 8d 2-mercaptoacetate) (trimethylolpropane tris (2-mercaptoacetate)), glycol di-3-mercaptopropionate represented by the following formula 8e (Glycol di-3-mercaptopropionate), and any combination thereof selected from the group consisting of can take one

[Formula 8a]

[Formula 8b]

[Formula 8c]

[Formula 8d]

[Formula 8e]

The thiol-based additive may be included in an amount of 0.1 wt % to 10 wt %, for example, 0.1 wt % to 5 wt %, based on the total amount of the photosensitive resin composition. When the thiol-based additive is included within the above range, the stability of light conversion materials such as quantum dots can be improved, and the heat resistance of light conversion materials such as quantum dots can be improved by forming a covalent bond by reacting with the thiol group in the component with the acrylic group of the resin or monomer. may have an effect.

The photosensitive resin composition according to an embodiment includes a polymerization inhibitor in addition to the thiol-based additive; malonic acid; 3-amino-1,2-propanediol; silane-based coupling agents; leveling agent; fluorine-based surfactants; or a combination thereof.

The polymerization inhibitor may include a hydroquinone-based compound, a catechol-based compound, or a combination thereof, but is not necessarily limited thereto. As the composition according to one embodiment further includes the hydroquinone-based compound, the catechol-based compound, or a combination thereof, crosslinking at room temperature may be prevented during exposure after printing (coating) the composition.

For example, the hydroquinone-based compound, the catechol-based compound, or a combination thereof is 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, pyroga Lol, 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, the catechol-based compound, or a combination thereof may be used in the form of a dispersion, and the polymerization inhibitor in the dispersion form is present in an amount of 0.001% to 3% by weight, for example, 0.1% to 2% by weight, based on the total amount of the composition. can be included as When the polymerization inhibitor is included within the above range, it is possible to solve the problem of aging at room temperature and to prevent sensitivity deterioration and surface peeling.

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

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, γ glycidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

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

In addition, the photosensitive resin composition may further include a surfactant, such as a fluorine-based surfactant, to improve coating properties and prevent defect formation, if necessary.

As the fluorine-based surfactant, BM Chemie's BM-1000 ^® , BM-1100 ^® , etc.; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® and the like of Dainippon Inki Kagaku Kogyo Co., Ltd.; Sumitomo 3M Co., Ltd.'s Prorad FC-135 ^® , the same FC-170C ^® , the same FC-430 ^® , the same FC-431 ^® , etc.; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® and the like of Asahi Grass Co., Ltd.; SH-28PA ^® , Copper-190 ^® , Copper-193 ^® , SZ-6032 ^® , SF-8428 ^® and the like from Toray Silicone Co., Ltd.; Fluorine-based surfactants commercially available under names such as F-482, F-484, F-478, and F-554 from DIC Co., Ltd. may be used.

The fluorochemical surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the fluorine-based surfactant is included within the above range, coating uniformity is secured, stains do not occur, and wettability to a glass substrate is excellent.

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

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

The manufacturing method of the photosensitive resin film is as follows.

(1) coating and coating film formation step

The above-described photosensitive resin composition is applied to a predetermined pre-treated substrate to a desired thickness, for example, 1.2 μm to 3.5 μm, by using a method such as a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, or the like. After coating, the solvent is removed by heating at a temperature of 70° C. to 90° C. for 1 minute to 10 minutes to form a coating film.

(2) exposure step

For pattern formation required for the obtained coating film, after passing through a mask of a predetermined shape, actinic rays of 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. may be used, and in some cases, X-rays, electron beams, etc. may be used.

The exposure amount varies depending on the type, compounding amount, and dry film thickness of each component of the photosensitive resin composition, but is, for example, 500 mJ/cm ² or less (by a 365 nm sensor) when a high-pressure mercury lamp is used.

(3) Development stage

Following the exposure step, an alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions, thereby leaving only the exposed portion to form an image pattern.

(4) post-processing step

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

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

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

(Manufacture of cardo-based binder resin)

Synthesis Example 1-1

138g of 9,9'-bis(4-glyciloxyphenyl)fluorene (Hear chem), 54g 4-(methylthio)benzenethiol (TCI), benzyltriethylammonium chloride (Daejeong Chemical Co., Ltd.) Company) 1.4g, triphenylphosphine (Aldrich) 1g, propylglycolmethylethylacetate (Daicel Chemical) 128g, and hydroquinone 0.5g were added, heated to 120°C, maintained for 12 hours, and the following formula A-1 was obtained. The indicated compounds were synthesized.

[Formula A-1]

Synthesis Example 2-1

In a reactor, 60 g of the compound represented by Formula A-1, 16 g of 3,3',4,4'-thiodiphthalic anhydride (American chemical), 5-norborene-2,3-dicarboxylic anhydride ( TCI Co.) 3.4g, propyl glycol methylethyl acetate (Daicel Chemical Co.) 20g and N,N'-tetramethylammonium chloride 0.1g were added, the temperature was raised to 120°C, maintained for 2 hours, and the compound represented by the following formula B-1 (weight average molecular weight: 5,600 g/mol) was synthesized.

[Formula B-1]

Synthesis Example 2-2

In a reactor, 60 g of the compound represented by Formula A-1, 16 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (TCI), 5-norborene-2,3-dicarboxylic anhydride (TCI Company) 3.4 g, 20 g of propyl glycol methyl ethyl acetate (Daicel Chemical) and 0.1 g of N, N'-tetramethylammonium chloride were added, heated to 120 ° C, maintained for 2 hours, and the compound represented by the following formula B-2 ( Weight average molecular weight: 4,300 g/mol) was synthesized.

[Formula B-2]

(Preparation of photosensitive resin composition)

Examples 1 to 8 and Comparative Examples 1 to 3

Photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1 using the components mentioned below.

Specifically, after dissolving the photopolymerization initiator in a mixed solvent of cyclohexyl acetate and propylene glycol methyl ether acetate, the mixture was sufficiently stirred at room temperature for 2 hours. Subsequently, a photopolymerizable monomer and a binder resin were added, followed by stirring at room temperature for another 1 hour. Thereafter, the quantum dot dispersion was mixed with the mixed solvent in which the photopolymerization initiator was dissolved, and a dispersing agent, a thiol-based additive, and a fluorine-based surfactant were added thereto, followed by stirring at room temperature for 1 hour, and filtering the product three times. By removing the impurities, a photosensitive resin composition was prepared.

(A) quantum dots

InP/ZnS quantum dots (fluorescence λ _em =535nm, FWHM=40nm, Green QD, Hansol Chemical)

(B) binder resin

(B-1) cardo binder resin

(B-1-1) Cardo-based binder resin prepared in Synthesis Example 2-1

(B-1-2) Cardo-based binder resin prepared in Synthesis Example 2-2

(B-2-1) Acrylic binder resin (SP-RY16, Showa Denko Co.)

(B-2-2) Epoxy-based binder resin (EHPE3150, Daicel Chemical Industry Co., Ltd.)

(C) photopolymerizable monomer

Dipentaerythritol hexaacrylate (Nippon Explosive Co., Ltd.)

(D) photopolymerization initiator

PBG305 (Tronyl Company)

(E) solvent

(E-1) Propylene glycol (mono) methyl ether acetate (PGMEA) (Sigma-Aldrich)

(E-2) cyclohexyl acetate (Sigma-Aldrich)

(E-3) pentyl acetate (Sigma-Aldrich)

(F) Diffusion agent

Titanium dioxide dispersion (TiO ₂ solid content 20% by weight, average particle diameter: 200nm, Dito Technology Co., Ltd.)

(G) other additives

(G-1) Thiol-based additive (glycol di-3-mercaptopropionate, Bruno BOCK Co.)

(G-2) Fluorine-based surfactant (F-554 (10%), DIC Co.)

(G-3) polymerization inhibitor (methylhydroquinone, TOKYO CHEMICAL Co.)

(Unit: % by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) quantum dots 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 12.8 (B) binder resin (B-1-1) 7.4 7.4 7.4 7.4 - - - - 7.4 7.4 7.4 (B-1-2) - - - - 7.4 7.4 7.4 7.4 - - - (B-2-1) 5.2 5.2 5.2 - 5.2 5.2 5.2 - 5.2 5.2 5.2 (B-2-2) - - - 5.2 - - - 5.2 - - - (C) photopolymerizable monomer 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 1.9 (D) photopolymerization initiator 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E) solvent (E-1) 40.2 24.0 13.4 24.0 40.2 24.0 13.4 24.0 6.7 60.3 24.0 (E-2) 26.8 43.0 53.6 43.0 26.8 43.0 53.6 43.0 60.3 6.7 - (E-3) - - - - - - - - - - 43.0 (F) Diffusion agent 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (G) other additives (G-1) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 (G-2) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 (G-3) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Total 100 100 100 100 100 100 100 100 100 100 100

Evaluation 1: Patternability evaluation after development

The photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 were coated on a glass substrate to a thickness of 3 μm using a spin coater (Mikasa, Opticoat MS-A150), respectively, and then coated with a hot plate (hot plate). -plate) for 120 seconds at 80 ° C., and soft-baking was performed, and exposure was performed with a power of 60 mJ using an exposure machine (Ushio, ghi broadband). Subsequently, it was developed with an aqueous solution of 0.2% by weight of potassium hydroxide (KOH) using a developing machine (SVS, SSP-200). Thereafter, the cross section and surface of the pattern remaining after development were measured at a magnification of 20,000 times using a focused ion beam (FIB) scanning electron microscope (SEM), and the results are shown in Tables 2 and 3 below. (The number of pinholes on the pattern surface is visually observed)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Whether or not there is an undercut on the pattern cross section after developing ○ ○ ○ ○ ○ ○ ○ ○ △ ⅹ ⅹ

(○: no undercut phenomenon was observed

△: A little undercut phenomenon was observed

ⅹ: severe undercut phenomenon observed)

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Patternability according to the number of pinholes in the pattern surface after development ○ ○ ○ ○ ○ ○ ○ ○ ⅹ ⅹ ⅹ

(○: No pinholes observed with the naked eye

△: The number of pinholes observed with the naked eye is 1 or more and less than 10

ⅹ: 10 or more pinholes observed with the naked eye)

From Tables 2 and 3, it can be seen that the photosensitive resin film prepared using the photosensitive resin composition according to Examples has better pattern characteristics after development than the photosensitive resin film prepared using the photosensitive resin composition according to Comparative Example. .

Evaluation 2: Evaluation of light absorption rate after thermal process

The photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 were coated on a glass substrate to a thickness of 10 μm using a spin coater (Mikasa, Opticoat MS-A150), and then coated with a hot plate (hot plate). -plate) for 120 seconds at 80 ° C., and soft-baking was performed, and exposure was performed with a power of 60 mJ using an exposure machine (Ushio, ghi broadband). Subsequently, it was developed with a 0.2% by weight potassium hydroxide (KOH) aqueous solution using a developing machine (SVS, SSP-200). Thereafter, hard-baking was performed in a convection oven at 180° C. for 30 minutes, respectively. After hard-baking with QE-2100, a quantum efficiency meter of Otsuka Electronics, the light absorption and light conversion rates of the single film were measured in an oven at 50 ° C., and after 15 days, the light absorption and light conversion rate of the single film were measured again. The results are shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Light absorption rate (%) 92.8 93.3 92.3 92.5 92.9 93.5 92.2 92.4 88.5 81.4 92.9 Light conversion rate (%) 32.7 33.1 32.2 32.7 32.8 33.5 32.3 32.8 30.5 23.5 32.9 Single film wavelength (nm) 537.2 537.6 536.8 536.9 536.8 537.1 537.4 537.2 536.8 547.2 536.7

As shown in Table 4, the photosensitive resin films prepared using the photosensitive resin compositions according to Examples 1 to 8 and Comparative Example 3 were prepared using the photosensitive resin compositions according to Comparative Examples 1 and 2. It can be confirmed that the optical properties of the quantum dots are not significantly lowered than those of the photosensitive resin film even after the thermal process.

The present invention is not limited to the above embodiments, but can be manufactured in a variety of different forms, and those skilled in the art to which the present invention pertains may take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented with Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (14)

(A) quantum dots;
(B) a binder resin;
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator;
(E-1) a first solvent; and
(E-2) a second solvent different from the first solvent
including,
The second solvent is cyclohexyl acetate,
The second solvent is included in 40% to 80% by weight based on the total amount of the first solvent and the second solvent,
The binder resin includes a cardo-based binder resin and an acrylic binder resin including a structural unit represented by Formula 1 below,
The photosensitive resin composition in which the cardo-based binder resin is included in a greater content than the acrylic-based binder resin:
[Formula 1]

In Formula 1,
R ¹¹ and R ¹² are each independently represented by Formula 2 below;
[Formula 2]

In Formula 2,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group;
L ² is an oxygen atom or a sulfur atom;
R ¹ is "a C1 to C10 alkyl group substituted with a C1 to C10 alkylthio group" or "a C6 to C20 aryl group substituted with a C1 to C10 alkylthio 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 (where R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following Any one of the linking groups represented by Formula 1-1 to Formula 1-11;
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In Formula 1-5,
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 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

Z ² is an acid anhydride residue;
t1 and t2 are each independently an integer of 0 to 4.
According to claim 1,
The first solvent is a photosensitive resin composition having a lower boiling point than the second solvent.
delete According to claim 1,
The cardo-based binder resin has a weight average molecular weight of 2,000 g / mol to 20,000 g / mol photosensitive resin composition.
According to claim 1,
The photosensitive resin composition of claim 1 , wherein the binder resin further comprises at least one binder resin selected from the group consisting of an acrylic binder resin and an epoxy binder resin.
According to claim 1,
The photosensitive resin composition further comprises (F) 0.5% by weight to 10% by weight of a diffusing agent based on the total amount of the photosensitive resin composition.
According to claim 6,
The diffusing agent is a photosensitive resin composition comprising barium sulfate, calcium carbonate, titanium dioxide, zirconia or a combination thereof.
According to claim 1,
The photosensitive resin composition further comprises a thiol-based additive.
According to claim 8,
The thiol-based additive is a photosensitive resin composition comprising at least two or more functional groups represented by the following formula (7) at the terminal:
[Formula 7]

In Formula 7,
L ⁷ and L ⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 arylene group. It is a C2 to C20 heteroarylene group.
According to claim 1,
The quantum dot is a photosensitive resin composition of a quantum dot that absorbs light of 360 nm to 780 nm and emits fluorescence at 500 nm to 700 nm.
According to claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition,
1% to 50% by weight of the (A) quantum dots;
1% to 20% by weight of the (B) binder resin;
1% to 10% by weight of the (C) photopolymerizable monomer;
0.01% to 5% by weight of the (D) photopolymerization initiator; and
The remaining amount of the above (E) solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition may include a polymerization inhibitor; malonic acid; 3-amino-1,2-propanediol; silane-based coupling agents; leveling agent; fluorine-based surfactants; Or a photosensitive resin composition further comprising a combination thereof.
A photosensitive resin film prepared using the photosensitive resin composition of any one of claims 1, 2, and 4 to 12.
A color filter comprising the photosensitive resin film of claim 13.

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