KR20200061792A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

Provided are a photosensitive resin composition excellent in viscosity, light absorption, and resolution, a photosensitive resin film prepared by using the photosensitive resin composition, and a color filter including the photosensitive resin film. The photosensitive resin composition includes (A) quantum dots; (B) binder resin; (C) polymerizable monomer; (D) photopolymerization initiator; (E) light diffusing agent; (F) a compound represented by following Chemical formula 1; and (G) a solvent. [Chemical formula 1] In Chemical formula 1, each substituent is as defined in the specification.

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}

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film prepared using the photosensitive resin composition, and a color filter comprising the 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 to dissolve and remove non-exposed parts through a development process. The color filter material is alkali-soluble and requires high sensitivity, adhesion to a substrate, chemical resistance, and heat resistance. However, since the curing reaction is not sufficient by an exposure process, it is necessary to heat-cure it for a predetermined time at a high temperature of 200° C. or more in order to obtain required properties. Therefore, there are limitations in applications requiring low-temperature processes such as electronic paper and OLED.

On the other hand, in order to develop a photosensitive resin composition for a color filter that requires a relatively low-temperature process application 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, to the composition. Not enough, there is a problem of low reliability.

The above problem is a phenomenon that occurs because color materials such as pigments or dyes competitively absorb photopolymerization initiators and light energy, and it is also difficult to obtain sufficient initiation efficiency because it acts to remove the radicals generated by the pigments and dyes. The curing rate of the synthetic monomer is reduced than when the color material is not used.

Accordingly, a photosensitive resin composition containing a quantum dot, which can significantly improve reliability such as chemical resistance and heat resistance, has recently been attracting attention by using a quantum dot instead of a conventional dye or pigment.

In the case of a conventional photosensitive resin composition containing quantum dots, a light diffusing agent, such as titanium dioxide, which is a dispersion, is used to improve the absorption characteristics. When titanium dioxide is used, precipitation problems occur in the photosensitive resin composition containing quantum dots due to the particle size of titanium dioxide. When such precipitation occurs, it is difficult to ensure uniformity of the entire composition including the upper layer composition and the lower layer composition, and this non-uniformity makes it difficult to ensure the light absorption of the photosensitive resin composition containing quantum dots, ultimately affecting the composition of the entire composition.

Accordingly, the present inventors have attempted to solve the problem of precipitation of the light diffusion agent such as titanium dioxide, and after a long study, form a micelle by forming hydrogen with the light diffusion agent such as titanium dioxide to prevent precipitation of the light diffusion agent. It has led to the development of a novel compound that can.

One embodiment is to provide a photosensitive resin composition containing quantum dots, excellent in viscosity, light absorption, resolution, residual film rate and chemical resistance.

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 includes (A) a quantum dot; (B) binder resin; (C) polymerizable monomers; (D) photopolymerization initiator; (E) light diffusion agents; (F) a compound represented by the following formula (1); And (G) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ is a substituted or unsubstituted C5 to C20 alkylene group,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

R ² to R ⁵ may be each independently a methyl group.

The L ² may be a substituted or unsubstituted C6 to C20 arylene group.

The compound represented by Chemical Formula 1 may be included in an amount of 1 to 5% by weight based on the total amount of the photosensitive resin composition.

The light diffusing agent may be titanium dioxide.

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

The polymerizable monomer may include a (meth)acrylate-based compound, an oxetane-based compound, a thiol group-containing compound, or a combination thereof.

The photosensitive resin composition may further include a thermal polymerization initiator, a curing accelerator, or a combination thereof.

The photosensitive resin composition, the (A) quantum dot 1% to 40% by weight; (B) 1 to 30% by weight of the binder resin; (C) 0.5% to 20% by weight of the polymerizable monomer; (D) 0.1 to 5% by weight of the photopolymerization initiator; (E) 0.1 to 20% by weight of the light diffusing agent; (F) 1 to 5% by weight of the compound represented by the formula (1); And a residual amount of the (G) solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or (meth)acryloxy group; Leveling agents; Fluorine-based surfactants; Or a combination of these may be further included.

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

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

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

By using a compound capable of hydrogen bonding with a light-diffusing agent in the composition, the compound forms a Michel surrounding the light-diffusing agent through hydrogen bonding to prevent precipitation of the light-diffusing agent, ultimately As a result, it is possible to provide a photosensitive resin composition having excellent storage stability and the like.

1 is a schematic diagram showing a complex (Michel) of a light diffusing agent and a compound that has hydrogen bonds with the light diffusing agent in the middle.
FIG. 2 is a photograph in which the photosensitive resin composition according to Example 1 is coated on a substrate, and the pattern resolution is evaluated after exposure and development.
Figure 3 is a photo of the photosensitive resin composition according to Example 2 on the substrate, after coating, exposure and development to evaluate the pattern resolution.
Figure 4 is a photo of the photosensitive resin composition according to Example 3 on the substrate, after coating, exposure and development to evaluate the pattern resolution.
FIG. 5 is a photograph in which the photosensitive resin composition according to Comparative Example 1 was coated on a substrate, and the pattern resolution was evaluated after exposure and development.
FIG. 6 is a photograph in which the photosensitive resin composition according to Comparative Example 2 was coated on a substrate, exposed, and developed to evaluate pattern resolution.

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 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, 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, and "arylalkyl group" means a C6 to C20 arylalkyl group, and an "alkylene group" Column C1 to C20 means an 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 Means an arylene group, and "alkoxyl group" means a C1 to C20 alkoxyl group.

Unless otherwise specified herein, "substitution" means 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 salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt 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, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

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

Also, unless otherwise specified herein, “(meth)acrylate” means that both “acrylate” and “methacrylate” are possible, and “(meth)acrylic acid” means “acrylic acid” and “methacrylic acid”. "It means both are possible.

Unless otherwise specified in this specification, "combination" means mixing or copolymerization.

Unless otherwise defined in the chemical formula in the present specification, 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, cardo-based resin means a resin in which at least one functional group selected from the group consisting of the following Chemical Formulas 3-1 to 3-11 is included in the backbone in the resin.

Also, unless otherwise specified in this specification, "*" refers to a part connected to the same or different atom or chemical formula.

The photosensitive resin composition according to an embodiment includes (A) a quantum dot; (B) binder resin; (C) polymerizable monomers; (D) photopolymerization initiator; (E) light diffusion agents; (F) a compound represented by the following formula (1); And (G) a solvent.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

L ¹ is a substituted or unsubstituted C5 to C20 alkylene group,

L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

A color filter using a photosensitive resin composition can be mainly produced by coating three or more colors on a transparent substrate by dyeing, electrodeposition, printing, pigment dispersion, etc. Recently, the pigment dispersion technology has been improved to provide excellent color reproducibility. Pigment dispersion methods that ensure durability against heat, light, and humidity are mainly used. The color filter by the pigment dispersion method uses pigment refinement and surface treatment to realize high luminance and high contrast ratio, or recently, a high-performance color filter using a dye has been developed. In addition, various types of substrates are being used for flexible display, and in particular, it is necessary to develop a color filter that satisfies limited process conditions for the production of color filters in organic plastic substrates.

Accordingly, recently, a photosensitive resin composition using a quantum dot instead of a conventional dye or pigment as a colorant has attracted much attention. However, quantum dots have a higher instability than dyes or pigments, and when a photosensitive resin composition containing quantum dots is left at a high temperature for a long period of time, the viscosity change of the composition becomes large, storage stability is deteriorated, and light absorption is also lowered.

The quantum dot-containing photosensitive resin composition according to an embodiment may dramatically improve storage stability and light absorption of the quantum dot-containing photosensitive resin composition by using the compound represented by Chemical Formula 1, and furthermore, resolution, residual film rate, and chemical resistance Can be improved.

In addition, the photosensitive resin composition according to an embodiment may be used by mixing three different compounds ((meth)acrylate-based compounds, oxetane-based compounds, and thiol group-containing compounds) as polymerizable monomers, together with sulfonium-based cations Since an initiator may be additionally included, excellent resolution and durability can be secured only by a low temperature curing process.

Further, the photosensitive resin composition according to an embodiment may further include a curing accelerator, wherein the curing accelerator promotes a thermosetting reaction of the photosensitive resin composition, thereby preventing pattern damage and dropout that may occur during the development process, thereby preventing high-resolution fine patterns. It is possible to implement. In addition, the flow of the pattern, which may occur in the post-baking process, is prevented to maintain the taper angle relatively high, and the cohesive force inside the pattern is improved to increase the adhesion of the pattern.

Each component will be described in detail below.

(F) Compound represented by Formula 1

The photosensitive resin composition according to an embodiment includes the compound represented by Chemical Formula 1.

The compound represented by Chemical Formula 1 is divided into a structure represented by Chemical Formula 1-1 and a structure represented by Chemical Formula 1-2, and the structure represented by Chemical Formula 1-1 forms a hydrogen bond with a light diffusing agent. When the micelle is formed, the inside of the micelle is formed, and the structure represented by the following Chemical Formula 1-2 forms the outside of the micelle when the micelle is formed.

[Formula 1-1]

[Formula 1-2]

The compound represented by the formula (1) is capable of hydrogen bonding with the light diffusing agent because the structure represented by the formula (1-1) has hydrophobicity, and the compound represented by the formula (1) and the light diffusing agent (titanium dioxide) When formed, it has the form shown in FIG. 1, and when it is expressed as a specific chemical formula, it has the form shown in the following schematic.

[scheme]

In general, the light-diffusing agent used in the photosensitive resin composition containing quantum dots is a compound having a large particle size such as titanium dioxide, and it is difficult to prevent precipitation of the light-diffusing agent with a general level additive. However, according to an embodiment, the compound represented by Chemical Formula 1 can form a large micelle morphology by forming hydrogen bonds with the light diffusing agent such as titanium dioxide, and the light diffusing agent having a large particle size Can effectively prevent precipitation.

For example, in Formula 1, R ² to R ⁵ may be each independently a methyl group.

For example, in Chemical Formula 1, L ² may be a substituted or unsubstituted C6 to C20 arylene group.

For example, the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

The compound represented by the formula (2) must have a sulfone salt at the terminal, and since the sulfone salt is well soluble in a solvent such as propylene glycol methyl ether acetate as well as water, the compound represented by the formula (2) is used for the solvent described later. It can have excellent solubility (dispersibility).

Precipitation of the light diffusing agent is prevented due to the hydrogen bonding force between the compound represented by Chemical Formula 1 and specifically the Chemical Formula 2 and the light diffusing agent (for example, titanium dioxide), and ultimately, it has excellent storage stability and light absorption even at high temperature. Can be.

The compound represented by Formula 1 may be included in 1% by weight to 5% by weight, for example, 2% by weight to 4% by weight relative to the total amount of the photosensitive resin composition. When the compound represented by Chemical Formula 1 is included within the above range, it is possible to sufficiently prevent precipitation of the light diffusing agent by hydrogen bonding with the light diffusing agent, and further improves solubility in a solvent, thereby providing excellent storage stability and dispersibility. Can be obtained.

(A) Quantum dots

The quantum dot has a core-shell structure, and the shell may include Zn.

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

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

The quantum dots may be each independently an organic material or an inorganic material or a hybrid (mixed material) 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 shell are each independently a core composed of II-IV, III-V, etc., core/shell, core/first shell/ It may have a structure of a second shell, an alloy, an alloy/shell, and the like, 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. , It is not necessarily limited to this. 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 limited thereto.

In one embodiment, since interest in the environment has been greatly increased worldwide and regulations for toxic substances have been strengthened, in place of a luminescent material having a cadmium-based core, the quantum yield is somewhat low but eco-friendly. A non-cadmium-based light emitting material (InP/ZnS, InP/ZeSe/ZnS, etc.) was used, but is not limited thereto.

In the case of the quantum dots of the core/shell structure, the size (average particle size) of the quantum dots including the shell may be 5 nm to 15 nm, for example, 5 nm to 10 nm.

Meanwhile, for dispersion stability of the quantum dots, the photosensitive resin composition according to one embodiment may further include a dispersing agent. The dispersant helps to uniformly disperse the photoconversion material such as quantum dots in the photosensitive resin composition, and any nonionic, anionic or cationic dispersant 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 can 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% to 100% by weight, such as 10% to 20% by weight, based on the solid content of the photoconversion material such as quantum dots.

The quantum dots may be included from 1% by weight to 40% by weight, for example, 3% by weight to 30% by weight based on solids based on the total amount of the photosensitive resin composition. When the quantum dots are included within the above range, the light conversion rate is excellent and the pattern characteristics and development characteristics are not impaired, and thus excellent processability can be obtained.

(B) Binder resin

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

When the binder resin includes a cardo-based binder resin, the developability of the photosensitive resin composition is excellent, and the sensitivity during photocuring is good, and thus, the fine pattern formation property is excellent.

For example, the cardo-based binder resin may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ¹⁰³ and R ¹⁰⁴ 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 ¹⁰⁷ R ¹⁰⁸ , SiR ¹⁰⁹ R ¹¹⁰ (where R ¹⁰⁷ to R ¹¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or Formula 3-1 to any one of the linking group represented by Formula 3-11,

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

(In the above formula 3-5,

R ^z 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 3-6]

[Formula 3-7]

[Formula 3-8]

[Formula 3-9]

[Formula 3-10]

[Formula 3-11]

Z ² is an acid anhydride residue or an acid anhydride residue,

z1 and z2 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 is well formed without residue when manufacturing the light-shielding layer, there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may include a functional group represented by the following Chemical Formula 4 on at least one of both terminals.

[Formula 4]

In Chemical Formula 4,

Z ³ may be represented by the following formulas 4-1 to 4-7.

[Formula 4-1]

(In Formula 4-1, R ^h and R ⁱ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In Formula 4-5, R ^j 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 4-6]

[Formula 4-7]

The cardo-based binder resin includes, for example, fluorene-containing compounds such as 9,9-bis(4-oxiranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid anhydride, pyromellitic dihydride, cyclobutanetetracarboxylic acid anhydride, pe Anhydride compounds such as lenetetracarboxylic acid anhydride, tetrahydrofurantetracarboxylic acid anhydride, 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, and benzyltriethylammonium chloride.

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

The acrylic binder resin may include structural units represented by the following Chemical Formulas 5-1 to 5-5.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

In Chemical Formulas 5-1 to 5-5,

R ¹⁰ to R ¹⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to 10 alkoxy group,

L ⁹ is a substituted or unsubstituted C1 to C5 alkylene group,

p is an integer of 0 or 1.

The acrylic binder resin includes structural units represented by Chemical Formulas 5-1 to 5-5, and can control the developability of a pattern while ensuring high heat resistance and high luminance characteristics, and when used together with the cardo resin, By increasing the adhesion of the pattern, a fine pattern can be realized, has a high resolution, and can also secure a high transmittance.

The epoxy-based binder resin may include, but is not limited to, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or combinations thereof.

For example, the epoxy-based binder resin may include a structural unit represented by Formula 6 below.

[Formula 6]

The photosensitive resin composition may include the binder resin in 1% to 30% by weight, for example, 3% to 20% by weight. When the binder resin is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(C) polymerizable monomer

The polymerizable monomer may include a (meth)acrylate-based compound, an oxetane-based compound, a thiol group-containing compound, or a combination thereof.

For example, the polymerizable monomer is a (meth)acrylate-based compound represented by the following formula (7) (photopolymerizable monomer), an oxetane-based compound represented by the following formula (8) and a thiol group-containing compound represented by the following formula (9) (Photo/thermopolymerizable monomer).

[Formula 7]

[Formula 8]

[Formula 9]

In Chemical Formulas 7 to 9,

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

R ³ is a substituted or unsubstituted C1 to C20 alkyl group, L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ⁵ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The polymerizable monomer may include an oxetanyl group, a thiol group, and a (meth)acrylate group to increase the curing degree during photocuring and thermal curing.

Specifically, by using an oxetane-based compound that is a thermally polymerizable monomer, the reactivity of the thermal polymerization initiator, which will be described later, can be greatly improved, and by further using a thiol group-containing compound that can serve as both a photopolymerizable monomer and a thermally polymerizable monomer The crosslinking efficiency can be further improved. Furthermore, by using a sulfonium-based compound instead of a peroxide-based compound commonly used as a thermal polymerization initiator, the reactivity of the oxetanyl group can be greatly improved.

In addition, the thiol group-containing compound represented by the formula (9) is located in the middle of the thiol group rather than the end of the compound, it is possible to solve the odor problem occurring during the color filter process.

In addition, the (meth)acrylate-based compound represented by the formula (7) used as a photopolymerizable monomer has an ethylenically unsaturated double bond, thereby causing sufficient polymerization during exposure in a pattern forming process, resulting in excellent heat resistance, light resistance and chemical resistance pattern Can form.

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

The polymerizable monomer may be included in the photosensitive resin composition at 0.5% to 20% by weight, such as 1% to 15% by weight. When the polymerizable monomer is included within the above range, curing is sufficiently performed during exposure in the pattern forming process, and reliability is excellent, and heat resistance, light resistance, chemical resistance, resolution, and adhesion of the pattern are also excellent.

(D) Photopolymerization initiator

The photopolymerization initiator may be used as an initiator generally 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, and the like. .

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, and the like.

Examples of the benzophenone-based compound, benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4 And'-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- And chlorothioxanthone.

Examples of the benzoin-based 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, 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(trichloro methyl)-s-triazine , 2-biphenyl-4,6-bis(trichloro methyl)-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 And bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and the like. .

Examples of the oxime-based compound are 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-based 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 and 1-(4-phenylsulfanylphenyl)-butane-1-one oxime- O-acetate　 can be used.

In addition to the above compounds, the photopolymerization initiator may use carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, biimidazole compounds, fluorene compounds, and the like.

The photopolymerization initiator may be used together with a photosensitizer that causes a chemical reaction by absorbing light, becoming excited, and transmitting its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be heard.

The photopolymerization initiator may be included in the photosensitive resin composition in an amount of 0.1% to 5% by weight, such as 0.5% to 3% by weight. When the photopolymerization initiator is included within the above range, a pattern having excellent resolution without a residual film can be obtained due to an excellent balance of sensitivity and developability during exposure.

(E) Light diffusion agent

Meanwhile, the photosensitive resin composition further includes a light diffusion agent.

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

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

The light 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 light-diffusing agent is within the above range, it may have a better light-diffusing effect and may increase light conversion efficiency.

The light-diffusing agent may be included in an amount of 0.1% to 20% by weight, for example, 1% to 15% by weight based on solids based on the total amount of the photosensitive resin composition. When the light diffusing agent is included in an amount of less than 0.1% by weight, it is difficult to expect an effect of improving the light conversion efficiency by using the light diffusing agent, and when it exceeds 20% by weight, there is a fear that the pattern characteristics are deteriorated.

(G) solvent

The solvent has compatibility with the quantum dot, the binder resin, the polymerizable monomer, the photopolymerization initiator, a thermal polymerization initiator described below, and a curing accelerator described below, but materials that do not react may be used.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether and ethylene glycol ethyl 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 methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; 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 esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxy propionic acid alkyl esters such as methyl 3-oxy propionate and ethyl 3-oxy propionate; 3-alkoxy propionic acid alkyl esters such as methyl 3-methoxy propionate, ethyl 3-methoxy propionate, ethyl 3-ethoxy propionate and methyl 3-ethoxy propionate; 2-oxy propionic acid alkyl esters, such as methyl 2-oxy propionate, ethyl 2-oxy propionate, and propyl 2-oxy propionic acid; 2-alkoxy propionic acid alkyl esters such as methyl 2-methoxy propionate, ethyl 2-methoxy propionate, ethyl 2-ethoxy propionate, and methyl 2-ethoxy propionate; 2-oxy-2-methyl propionic acid esters such as methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methyl propionate, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; And ketone acid esters such as ethyl pyruvate, and N-methylformamide, N,N-dimethylformamide, N-methylformanirad, N-methylacetamide, and N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid And high-boiling solvents such as ethyl, diethyl oxalate, diethyl maleate, γ butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, ketones such as cyclohexanone are considered in consideration of compatibility and reactivity; Glycol ethers such as ethylene glycol ethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol methyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in the remaining amount with respect to the total amount of the photosensitive resin composition, for example, may be included in 20% to 80% by weight, for example, 35% to 80% by weight. When the solvent is included within the above range, as the photosensitive resin composition has an appropriate viscosity, it may have excellent coating properties when coating a large area using spin coating and slits.

(H) Thermal polymerization initiator

The photosensitive resin composition according to an embodiment may further include a thermal polymerization initiator.

For example, the thermal polymerization initiator may be a sulfonium-based cationic initiator, and the sulfonium-based cationic initiator may be included in a range of 0.01% by weight to 1% by weight based on the total amount of the photosensitive resin composition.

When the cationic initiator is included in the above range, it may have excellent pattern forming properties.

The sulfonium-based cationic initiator may be used to have an endothermic peak at a temperature during a post-baking process, for example, a temperature of less than 200°C, for example, a temperature of 100°C to 170°C, as measured by differential scanning calorimetry. In the case of a sulfonium-based cationic initiator having an endothermic peak of 200°C or higher by differential scanning calorimetry, the sulfonium-based cationic initiator is thermally decomposed at a temperature equal to or higher than the thermal curing temperature of the photosensitive resin composition at 200°C or higher. In addition, the sulfonium-based cationic initiator cannot serve to polymerize the binder resin, such as the epoxy resin and/or acrylic resin in the binder resin, before the thermal curing of the photosensitive resin composition, or the reaction rate becomes too slow. Accordingly, when the photosensitive resin composition is cured, the epoxy-based resin is polymerized, so that it cannot play a role of holding the photosensitive resin film or the like, and the above object cannot be achieved.

The sulfonium-based cationic initiator may include, for example, a compound represented by Formula 10 below.

[Formula 10]

In Chemical Formula 10,

R ⁶ to R ⁹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted A substituted C2 to C20 heteroaryl group or a combination thereof,

m is an integer from 0 to 6,

n is an integer from 0 to 5.

As described above, the sulfonium-based cationic initiator promotes a polymerization reaction of the binder resin, for example, an epoxy-based resin and/or an acrylic resin in the binder resin, thereby realizing a high-resolution fine pattern. For example, the polymerization reaction of the epoxy-based resin is composed of a thermal decomposition (or photolysis) step of the sulfonium-based cationic initiator, an initiation step, and a polymerization step, and each step is shown in Reaction Schemes 1 to 3 below.

[Scheme 1]

[Scheme 2]

[Scheme 3]

In Reaction Schemes 1 to 3, R ⁶ to R ⁹ , R ^x and R ^y are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, A substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or a combination thereof, w is the number of moles of the epoxy-based binder resin participating in the reaction, and m is an integer from 0 to 6 .

(I) Curing accelerator

The photosensitive resin composition according to one embodiment may further include a curing accelerator.

The curing accelerator may promote a curing reaction, such as a thermosetting reaction, between a polymerizable monomer and a binder resin, such as an epoxy resin and/or an acrylic resin in the binder resin.

The curing accelerator may be included in an amount of 0.1% to 3% by weight based on the total amount of the photosensitive resin composition. When the curing accelerator is included in an amount of less than 0.1% by weight based on the total amount of the photosensitive resin composition, the curing speed is slowed, the resolution of the pattern is poor, the taper angle cannot be formed high, and the curing accelerator is 3% by weight relative to the total amount of the photosensitive resin composition. When included in excess of %, the curing rate becomes faster than necessary, and in the post-baking process, not only the straightness deteriorates due to the excessive melting characteristic deterioration, but also the adhesion force decreases.

The curing accelerator may be an imidazole-based curing accelerator, and the imidazole-based curing accelerator may be represented by Formula 11 below.

[Formula 11]

In Chemical Formula 11,

R ²⁰ to R ²³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

For example, the curing accelerator may be any one selected from the group consisting of 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, and combinations thereof.

(J) Other additives

The photosensitive resin composition according to one embodiment includes malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or (meth)acryloxy group; Leveling agents; Fluorine-based surfactants; Or a combination of these may be further included.

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-based coupling agent include trimethoxysilyl benzoic acid, γmethacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γisocyanate propyl triethoxysilane, γglycidoxypropyl Trimethoxysilane, β-epoxycyclohexyl)ethyl trimethoxysilane, and the like. These may be used alone or in combination of two or more.

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-based coupling agent is included within the above range, adhesion and storage properties are excellent.

In addition, the photosensitive resin composition may further include a surfactant, for example, a fluorine-based surfactant, for the purpose of improving coating properties and preventing defects.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Dai Nippon Inki Chemical Industry Co., Ltd. Mecca Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^®, etc.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The surfactant may be used in 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is secured, staining does not occur, and wetting of the glass substrate is excellent.

In addition, a certain amount of other additives such as antioxidants and stabilizers may be 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.

Another embodiment provides a color filter and a display device (eg, an organic light emitting device, etc.) including the photosensitive resin film. The manufacturing method of the color filter is as follows.

(1) Application and coating film forming step

To the desired thickness, for example, from 1.2 μm to 3.5 μm, by using a method such as spin or slit coating, roll coating, screen printing, or an applicator method, on the substrate on which the photosensitive resin composition is subjected to a predetermined pretreatment. After application, a coating film 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 a pattern necessary for the obtained coating film, after interposing a mask of a predetermined shape, active 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. In some cases, X-rays, electron beams, etc. may be used.

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

(3) Development stage

Following the exposure step, by using an alkaline aqueous solution as a developer, dissolving and removing unnecessary portions to form only an exposed portion to form an image pattern.

(4) Post-treatment step

In order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc., the image pattern obtained by the above-described phenomenon can be cured by heating again or by irradiating with actinic rays.

By using the photosensitive resin composition described above, excellent heat resistance and chemical resistance can be obtained even at a low temperature process, and thus the photosensitive resin film manufactured using the photosensitive resin composition can be applied to a display device such as an organic light emitting device (OLED).

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

(Example)

(Production of a compound capable of forming Michelle through hydrogen bonding with a light diffusion agent)

Ergocalciferol (D2) (Aldrich Co.) (10 mol) and H3PO4 (0.1 mol) were added to tetrahydrofuran (THF) and a Distillation trap was installed and stirred at 80°C for 24 hours. Subsequently, Dodecylbenzenesulfonic acid sodium salt (Aldrich) (10 mol) was added to the solution, and MgBr (0.05 mol) was added after 1 hour, followed by stirring for 24 hours to obtain a reactant.

The reaction was stirred for 10 hours at room temperature (23° C.) in a 10% H 2 SO 4 aqueous solution, and then precipitated in n-Hexane to prepare a compound represented by the following Chemical Formula 2.

[Formula 2]

(Production of photosensitive resin composition)

Examples 1 to 3, Comparative Example 1 and Comparative Example 2

Photosensitive resin compositions according to each of Examples 1 to 3, Comparative Examples 1 and 2 were prepared with the compositions shown in Table 1 below using the components mentioned below.

Specifically, a photopolymerization initiator, a thermal polymerization initiator, a binder resin, and a thermal curing initiator were dissolved in a solvent, followed by stirring at room temperature for about 2 hours. Subsequently, an acrylic binder resin, a compound represented by Chemical Formula 2, a quantum dot, a light diffusing agent, and a polymerizable monomer were added and stirred at room temperature for 2 hours. After adding the additives 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.

(A) Coloring agent

InP/ZnSe/ZnS quantum dot dispersion (quantum dot solid content 30%, fluorescence λ _em =542nm, FWHM=36nm, Red QD, Hansol Chemical)

(B) Binder resin

(B-1) Cardo resin (V259ME, Shinil Iron Chemical Co., Ltd.)

  (B-2) Acrylic resin (Samsung SDI, 1000S)

(C) polymerizable monomer

  (C-1) Photopolymerizable monomer: dipentaerythritol hexaacrylate (Japan Chemical Co., DPHA)

  (C-2) Photo/thermopolymerizable monomer: a thiol group-containing compound (Showadenko, KarenzMT PE 1)

  (C-3) Thermopolymerizable monomer: oxetane-based compound (Toagosei, OXT-212)

(D) Photopolymerization initiator

  (D-1) OXE01 (BASF)

  (D-2) IRG369 (BASFf)

(E) Light diffusion agent

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

(F) Compound represented by Formula 2

(G) solvent

  Propylene glycol methyl ether acetate (PGMEA, Sigma-Aldrich)

(H) Thermal polymerization initiator

  TA-100 (San-Apro)

Other additives

  Leveling agent (DIC, F-554)

(Unit: weight%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (A) Quantum dots 53 53 53 53 53 (B) Binder resin (B-1) 1.18 1.18 1.18 5.68 1.18 (B-2) 3.25 3.25 3.25 3.25 7.75 (C) polymerizable monomer (C-1) 1.18 1.18 1.18 1.18 1.18 (C-2) 0.4 0.4 0.4 0.4 0.4 (C-3) 0.4 0.4 0.4 0.4 0.4 (D) Photopolymerization initiator (D-1) 0.1 0.1 0.1 0.1 0.1 (D-2) 1.04 1.04 1.04 1.04 1.04 (E) Light diffusion agent 6.75 10.75 10.75 6.75 6.75 (F) Compound represented by Formula 2 3.0 3.0 4.0 - - (G) solvent 29.58 25.58 24.58 28.08 28.08 (H) Thermal polymerization initiator 0.02 0.02 0.02 0.02 0.02 Other additives 0.1 0.1 0.1 0.1 0.1

Evaluation 1: viscosity evaluation

For each of the photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2, viscosity values were measured for each storage period (45° C., no humidity) using a viscometer (Brookfield's DV-IIRV-2 spindle, 23 rpm). Was measured, and the results are shown in Table 2 below.

(Unit: cP(mPa·s)) storage duration Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 0 days 4.7 4.8 4.9 5.0 5.4 2 days 4.7 4.9 5.0 5.2 6.3 7 days 4.8 5.0 5.0 8.2 7.8 15th 4.9 5.0 5.1 10.3 8.9 30 days 4.9 5.0 5.1 11.2 10.1

Evaluation 2: light absorption rate evaluation

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 were respectively spin coated on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150, 150 rpm) for 5 seconds, followed by a hot plate After baking for 2 minutes at 100℃ using (hot-plate), and irradiating UV with an output of 50 mJ/cm ² using an exposure machine (Ushio, ghi broadband), a quantum dot efficiency meter (OTSUKA, QE) -2100) to evaluate the light absorption rate for each storage period (at room temperature (25°C), non-humidity condition), and the results are shown in Table 3 below.

(unit: %) storage duration Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 0 days 88.12 94.34 94.62 88.21 88.11 2 days 88.12 94.35 94.60 88.17 88.09 7 days 88.10 94.30 94.60 88.01 87.82 15th 88.11 94.28 93.60 86.88 86.19 30 days 88.11 94.28 93.60 86.13 85.20

Evaluation 3: Resolution evaluation

After coating the photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, respectively, followed by hot plate (hot -plate) was soft-baked at 80°C for 120 seconds, and exposed at a power of 60 mJ using an exposure machine (Ushio, ghi broadband). Subsequently, it was developed with a 0.2% by weight aqueous potassium hydroxide (KOH) solution using a developer (SVS, SSP-200). Thereafter, the adhesion µm of the remaining pattern was checked through an optical microscope, and the results are shown in Table 4 and FIGS. 2 to 6.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Resolution (㎛) 30 30 20 40 50

Evaluation 4: Residual rate evaluation

After coating the photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, respectively, followed by hot plate (hot -plate) was soft-baked at 80°C for 120 seconds, and exposed at a power of 60 mJ using an exposure machine (Ushio, ghi broadband). Subsequently, it was developed with a 0.2% by weight aqueous potassium hydroxide (KOH) solution using a developer (SVS, SSP-200). Thereafter, hard-baking was performed in a convection oven at 100°C, 150°C, and 200°C for 30 minutes, respectively, and further cured at 200°C for 30 minutes. The coating, exposure, development, and the temperature of the pattern after hard-baking for each temperature and the height of the pattern after further curing were calculated to calculate the residual film ratio, and the results are shown in Table 5 below.

Residual rate evaluation criteria

○: Less than 3% residual film

△: Residual film reduction of 5% or less

X: Reduction of residual film exceeding 5%

100℃ 150℃ 200℃ Example 1 ○ ○ ○ Example 2 ○ ○ △ Example 3 ○ ○ ○ Comparative Example 1 △ △ ○ Comparative Example 2 X △ ○

Evaluation 5: Chemical resistance evaluation

After coating the photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 and 2 on a glass substrate using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, respectively, followed by hot plate (hot -plate) was soft-baked at 80°C for 120 seconds, and exposed at a power of 60 mJ using an exposure machine (Ushio, ghi broadband). Subsequently, it was developed with a 0.2% by weight aqueous potassium hydroxide (KOH) solution using a developer (SVS, SSP-200). Thereafter, hard-baking was performed at 100°C, 150°C, and 200°C for 20 minutes in a convection oven to obtain a patterned coating film.

The coating film was immersed in an NMP solvent at 80° C. for 2 minutes to evaluate chemical resistance, and the results are shown in Table 6 below.

The chemical resistance was evaluated as a color change (Δ) of the coating film before and after immersion in NMP solvent, and the color change (Δ was measured using a spectrophotometer (MCT3000, Otsuka Electronics Co., Ltd.).

Criteria for chemical resistance evaluation

○: Δ is 3% or less

Δ: Δ is 5% or less

Ⅹ: Δ exceeds 5%

100℃ 150℃ 200℃ Example 1 ○ ○ ○ Example 2 △ ○ ○ Example 3 ○ ○ ○ Comparative Example 1 △ △ △ Comparative Example 2 X △ △

As shown in Table 2, it is confirmed that the photosensitive resin composition according to one embodiment (Examples 1 to 3) is maintained at a high temperature of 45° C. for a long time without a viscosity change compared to the photosensitive resin compositions of Comparative Examples 1 and 2 Can be.

As shown in Table 3, the photosensitive resin composition according to an embodiment (Examples 1 to 3) has a longer light absorption rate than the photosensitive resin compositions of Comparative Examples 1 and 2 for a long period of time, and titanium dioxide It can be seen that the initial value is maintained even if the excess is included.

As shown in Table 4 and FIGS. 2 to 6, the photosensitive resin composition (Examples 1 to 3) according to one embodiment has excellent pattern resolution of 30 μm or less after development, but Comparative Example 1 and Comparative Example The photosensitive resin composition of 2 can be confirmed that the pattern resolution after development is inferior to 40 μm or more.

As shown in Table 5, the photosensitive resin composition according to one embodiment (Examples 1 to 3) has a uniform residual film reduction at low temperature as well as high temperature, but the photosensitive resin composition of Comparative Example 1 and Comparative Example 2 is low temperature It can be seen from the large residual film imbalance.

As shown in Table 6, the photosensitive resin composition according to one embodiment (Examples 1 to 3) has a uniform ΔEab* at low temperature as well as high temperature, but the photosensitive resin composition of Comparative Example 1 and Comparative Example 2 is low temperature. In addition, it can be seen that color change occurs even at high temperatures.

The present invention is not limited to the above embodiments, but may be manufactured in various different forms, and those skilled in the art to which the present invention pertains have other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that can be carried out. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (12)

(A) quantum dots;
(B) binder resin;
(C) polymerizable monomers;
(D) photopolymerization initiator;
(E) light diffusion agents;
(F) a compound represented by the following formula (1); And
(G) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁵ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ is a substituted or unsubstituted C5 to C20 alkylene group,
L ² is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group.
According to claim 1,
R ² to R ⁵ are each independently a methyl group photosensitive resin composition.
According to claim 1,
The L ² is a substituted or unsubstituted C6 to C20 arylene group photosensitive resin composition.
According to claim 1,
The compound represented by Formula 1 is a photosensitive resin composition contained in 1 to 5% by weight relative to the total amount of the photosensitive resin composition.
According to claim 1,
The photo-diffusion agent is a titanium dioxide photosensitive resin composition.
According to claim 1,
The binder resin is a photosensitive resin composition comprising a cardo-based binder resin, an acrylic-based binder resin or a combination thereof.
According to claim 1,
The polymerizable monomer is a (meth) acrylate-based compound, oxetane-based compound, a photosensitive resin composition comprising a thiol group-containing compound or a combination thereof.
According to claim 1,
The photosensitive resin composition further comprises a thermal polymerization initiator, a curing accelerator, or a combination thereof.
According to claim 1,
The photosensitive resin composition,
(A) 1 to 40% by weight of the quantum dot;
(B) 1 to 30% by weight of the binder resin;
(C) 0.5% to 20% by weight of the polymerizable monomer;
(D) 0.1 to 5% by weight of the photopolymerization initiator;
(E) 0.1 to 20% by weight of the light diffusing agent;
(F) 1 to 5% by weight of a compound represented by Formula 1; And
(G) Residual amount of solvent
Photosensitive resin composition comprising a.
According to claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or (meth)acryloxy group; Leveling agents; Fluorine-based surfactants; Or a photosensitive resin composition further comprising a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-10.
A color filter comprising the photosensitive resin film of claim 11.

Images