KR102237366B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) quantum dots; (B) binder resin; (C) photopolymerizable monomer; (D) photoinitiator; (E) light diffusing agent; And (F) a solvent, wherein the light diffusing agent comprises a photosensitive resin composition having a primary particle diameter of 80 nm to 200 nm and a secondary particle diameter of 120 nm to 250 nm, a photosensitive resin film prepared using the same, and the photosensitive resin film. A color filter is provided.

Description

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

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

In general, a color filter applied to a display forms a desired pattern through an exposure process in which a photomask is applied using a photosensitive resist composition, and a color filter is formed through a patterning process in which an unexposed part is dissolved and removed through a development process. The color filter material is alkali-soluble and requires high sensitivity, adhesion to the substrate, chemical resistance, and heat resistance. And, it is common to use a pigment or a dye as a color material.

However, pigments have excellent heat resistance or chemical resistance, but are not well dispersed in a solvent, so color characteristics such as luminance are not excellent, and dyes have excellent color characteristics, but have poor durability, so that heat resistance or chemical resistance is not excellent. .

Accordingly, the development of a new concept of a self-luminous type photosensitive resin composition capable of surpassing the technical limitations of a photosensitive resin composition using a pigment or dye as a color material and a color filter material applying the same has been continued.

One embodiment is to provide a photosensitive resin composition advantageous for sedimentation while maximizing a light absorption rate and a light conversion rate by controlling the primary particle diameter and the secondary particle diameter of the light diffusing agent.

Another embodiment is to provide a photosensitive resin film prepared by 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) binder resin; (C) photopolymerizable monomer; (D) photoinitiator; (E) light diffusing agent; And (F) a solvent, wherein the light diffusing agent provides a photosensitive resin composition having a primary particle diameter of 80 nm to 200 nm and a secondary particle diameter of 120 nm to 250 nm.

The light diffusing agent may have a primary particle diameter of 80 nm to 120 nm, and a secondary particle diameter of 160 nm to 230 nm.

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

The light diffusing agent may be a rutile type titanium dioxide.

The quantum dots may include a quantum dot, or a combination thereof having the maximum fluorescence wavelength (fluorescence λ _em) on the quantum dot, 580nm to 700nm with a maximum fluorescence wavelength (fluorescence λ _em) at 450nm to 580nm.

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

The thiol-based additive may be included in an amount of 1% to 10% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) quantum dots 1% by weight to 30% by weight; (B) 1% to 20% by weight of the binder resin; 1% to 20% by weight of the (C) photopolymerizable monomer; (D) 0.1% to 5% by weight of the photopolymerization initiator; (E) 2% to 15% by weight of the light diffusing agent; And 30% to 80% by weight of the (F) solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; It may further include a fluorine-based surfactant or a combination thereof.

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

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

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

The photosensitive resin composition containing quantum dots according to an embodiment includes a light diffusing agent having a controlled primary particle diameter and a secondary particle diameter, maximizing the scattering effect on the quantum dots, and allowing re-dispersion in a short time with a reduced density. Do. Accordingly, it becomes possible to realize high luminance and high color of the color pearly including the photosensitive resin film prepared by using the composition.

1 is a schematic diagram showing a primary particle diameter and a secondary particle diameter of a light diffusing agent.
2 is a scanning electron microscope (SEM) photograph of a light diffusing agent used in Example 3. FIG.
3 is a scanning electron microscope (SEM) photograph of a light diffusing agent used in Comparative Example 5. FIG.
4 is a graph of X-ray analysis of the crystal phase of the light diffusing agent used in Example 3. FIG.
5 is a graph of X-ray analysis of the crystal phase of the light diffusing agent used in Example 7. FIG.

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 in the specification, “alkyl group” refers to a C1 to C20 alkyl group, “alkenyl group” refers to a C2 to C20 alkenyl group, and “cycloalkenyl group” refers to a C3 to C20 cycloalkenyl group, , "Heterocycloalkenyl group" refers to a C3 to C20 heterocycloalkenyl group, "aryl group" refers to a C6 to C20 aryl group, and "arylalkyl group" refers to a C6 to C20 arylalkyl group, and "alkylene group" Refers to a C1 to C20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, and "heteroarylene group" refers to a C3 to C20 hetero It means an arylene group, and the "alkoxyl group" means a C1 to C20 alkoxyl group.

Unless otherwise specified in the specification, "substituted" 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 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 in the specification, "hetero" means that at least one hetero atom of at least one of N, O, S, and P is included in the formula.

In addition, unless otherwise specified in the specification, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth)acrylic acid" refers to "acrylic acid" and "methacrylic acid. "It means both are possible.

Unless otherwise specified in the 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, the cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 1-1 to 1-11 are included in the backbone of the resin.

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

Photosensitive resin composition according to one embodiment (A) quantum dots; (B) binder resin; (C) photopolymerizable monomer; (D) photoinitiator; (E) light diffusing agent; And (F) a solvent, wherein the light diffusing agent has a primary particle diameter of 80 nm to 200 nm, and a secondary particle diameter of 120 nm to 250 nm.

In general, the photosensitive resin composition is composed of a pigment or dye, a photopolymerizable monomer, a binder resin, a photopolymerization initiator, a solvent, and an additive, but the photosensitive resin composition according to an embodiment is an inorganic material to impart color characteristics instead of a pigment or dye. Quantum dots are put in. Since the color filter manufactured using the photosensitive resin composition according to the embodiment emits light, it is higher luminance compared to the color filter manufactured using the existing photosensitive resin composition, high efficiency for reducing power consumption, wide viewing angle, and high color reproducibility It has the advantage of having characteristics, and can ultimately contribute to the development of an LCD having the above characteristics.

The light diffusing agent helps to use the self-luminous properties of the quantum dots more efficiently, but due to the nature of inorganic materials, when acting in the photoresist, the linearity of the pattern decreases and developability is adversely affected. In addition, the light diffusing agent having a size larger than that of the quantum dot has a problem of adversely acting on sedimentation of the composition due to its high specific gravity. To solve this problem, efforts have been made to simultaneously take scattering properties and patterning properties by mixing two different types of light diffusing agents, but both were insufficient to solve the problem of sedimentation of the composition.

According to one embodiment, by limiting the primary particle diameter and the secondary particle diameter of the light diffusing agent used with the quantum dots to 80 nm to 200 nm and 120 nm to 250 nm, respectively, the scattering effect for the quantum dots is maximized, and at the same time, the sedimentation is reduced with a lower density. Solved the problem.

Specifically, when the primary particle diameter of the light diffusing agent is controlled to be 50 nm to 200 nm, the problem of sedimentation can be solved. That is, when the dispersed composition containing the light diffusing agent having a primary particle diameter limited to the above range is re-dispersed again, the composition is rapidly re-dispersed within a short time, and the sedimentation rate is slowed. When the primary particle diameter of the light diffusing agent is less than 80 nm (regardless of the secondary particle diameter control), the light absorption rate and the light conversion rate are lowered, and when the primary particle diameter of the light diffusing agent is more than 200 nm, the size is too large and the sedimentation rate is increased. It becomes too fast and negatively affects the roughness of the surface of the light diffuser particles.

In addition, when the primary particle diameter of the light diffusing agent is controlled within the above-described range and the secondary particle diameter is controlled to 120 nm to 250 nm, the sedimentation rate is slowed while maximizing optical characteristics, specifically, blue light absorption rate and blue light conversion rate. I can.

Hereinafter, each component will be described in detail.

(E) light Diffuser

As described above, the light diffusing agent has a primary particle diameter of 80 nm to 200 nm, and a secondary particle diameter of 120 nm to 250 nm. For example, the light diffusing agent may have a primary particle diameter of 80 nm to 120 nm, and a secondary particle diameter of 160 nm to 230 nm.

For example, the photosensitive resin composition according to an embodiment may further include a dispersion of a light diffusing agent in which the light diffusing agent is dispersed. As the dispersion in which the light diffusing agent is dispersed, any organic solvent such as PGMEA may be used without particular limitation.

For example, the light diffusing 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 (TiO ₂ ), for example, rutile type titanium dioxide. Titanium dioxide has a relatively high refractive index and can increase the self-luminescence efficiency of quantum dots of a photoresist. Furthermore, when the crystal phase of the titanium dioxide is a rutile type, optical characteristics may be increased compared to the case of an anatase type.

The light diffusing agent reflects light that is not absorbed by the quantum dots, and allows the reflected light to be absorbed again. That is, the light diffusing agent may increase the amount of light absorbed by the quantum dots, thereby increasing the light conversion rate of the quantum dots in the photosensitive resin composition. That is, it is possible to prevent a decrease in the blue light conversion rate due to the progress of the color filter process.

The light diffusing agent may be included in an amount of 2% to 15% by weight, such as 5% to 12% by weight, based on the total amount of the photosensitive resin composition based on the dispersion. That is, the light diffusing agent dispersion may be included in an amount of 2% to 15% by weight based on the total amount of the photosensitive resin composition. When the light diffusing agent is included in an amount of less than 2% by weight based on the total amount of the photosensitive resin composition, it is difficult to expect the effect of preventing the reduction of the light conversion rate due to the use of the light diffusing agent. The pattern characteristic of the photosensitive organic film is deteriorated, and as a result, the light conversion rate is lowered.

(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 450 nm to 700 nm. That is, the quantum dot may have a maximum fluorescence emission wavelength (fluorescence λ _em ) at 450 nm to 700 nm.

_{Specifically, the quantum dots are quantum dots (eg, green quantum dots) having a maximum fluorescence emission wavelength (fluorescence λ em} ) at 450 nm to 580 nm, quantum dots (eg, red quantum dots) having a maximum fluorescence emission wavelength (fluorescence λ _em ) at 580 nm to 700 nm, or Combinations of these may be included.

The green quantum dots may have an average particle diameter of 5 nm to 10 nm, and the red quantum dots may have an average particle diameter of 7 nm to 15 nm.

The quantum dots may have a full width at half maximum (FWHM) of 20 nm to 100 nm, such as 20 nm to 80 nm, such as 40 nm to 60 nm. When the quantum dots have a half width in the above range, the color purity is high, so that when used as a color filter material, there is an effect of having a high color reproducibility.

The quantum dot may be an organic material, an inorganic material, or a hybrid (mixed material) of an organic material and an inorganic material.

The quantum dot may be composed of a core and a shell surrounding the core, and the core and the shell are each independently a core composed of a group II-IV, a group III-V, a core/shell, a core/first shell/second shell , Alloy, alloy / shell, etc., may have a structure, 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. , 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 limited thereto.

The structure of the quantum dot is not particularly limited, but in the case of the core/shell structured quantum dot, the size (average particle diameter) of the entire quantum dot including the shell may be 1 nm to 15 nm, for example, 5 nm to 10 nm.

In order to improve the stability and dispersibility of the quantum dots, it is possible to stabilize the quantum dots by substituting an organic material on the shell surface, the organic material is a thiol-based compound, amine-based compound, phosphine oxide-based compound, acryl-based compound, Si-based It may include a compound and the like, but is not necessarily limited thereto.

Recently, as interest in the environment has increased greatly around the world and regulations on toxic substances have been strengthened, instead of a luminescent material having a cadmium-based core, it is an eco-friendly non-cadmium-based luminescent material with a rather low quantum yield. , For example, InP/ZnS core-shell type quantum dots, InP/ZnSe/ZnS core/first shell/second shell type quantum dots, etc. Although used, it is not necessary to use a non-cadmium-based light emitting material.

Meanwhile, for the 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 quantum dots in the photosensitive resin composition, and 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% to 100% by weight, such as 10% to 20% by weight, based on the solid content of the quantum dots.

The quantum dots may be included in an amount of 1% to 30% by weight based on the total amount of the photosensitive resin composition according to an embodiment. When the quantum dots are included within the above range, it is possible to prevent the occurrence of photoconversion characteristics inherent in the quantum dots and decrease in photoconversion efficiency.

(B) binder resin

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

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

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxy 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% to 50% by weight, such as 10% to 40% by weight, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; 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 The above can also be used in combination.

The weight average molecular weight of the acrylic binder resin may be 5,000 g/mol to 15,000 g/mol.　When the weight average molecular weight of the acrylic binder resin is within the above range, adhesion to the substrate is excellent, physical and chemical properties are good, and 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 resolution of the pixel pattern is excellent.

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

[Formula 1]

In Formula 1,

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

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

Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁷ R ¹⁸ , SiR ¹⁹ R ²⁰ (wherein R ¹⁷ to R ²⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following It is 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.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, for example, 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, a pattern can be formed well without residue when preparing a photosensitive organic film, 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 Formula 2 below at at least one of both ends.

[Formula 2]

In Chemical Formula 2,

Z ³ may be represented by the following Chemical Formulas 2-1 to 2-7.

[Formula 2-1]

(In Formula 2-1, 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 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

(In Formula 2-5, 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 2-6]

[Formula 2-7]

The cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis(4-oxyranylmethoxyphenyl)fluorene; Benzenetetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic acid dianhydride, phenol Anhydride compounds such as rylene tetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; Solvent compounds such as propylene glycol methylethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And two or more of amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, and benzyltriethylammonium chloride.

When the binder resin is a cardo-based binder resin, the photosensitive resin composition including the same has excellent developability, and has good sensitivity during photocuring and excellent fine pattern formation.

The binder resin may be included in an amount of 1% to 20% by weight, such as 3% to 15% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent sensitivity, film residual rate, developability, resolution, and straightness of the pattern can be obtained.

(C) Photopolymerization Monomer

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

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

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylol propane tri( Meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

For example, commercially available products of the photopolymerizable monomer are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^{®; KAYARAD TC-110S ®} of Nihon Kayaku Co., Ltd., TC-120S ^®, etc.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^{®; KAYARAD HDDA ®} , HX-220 ^® , R-604 ^{® of} Nihon Kayaku Co., Ltd.; Osaka Yuki Kagaku High School Co., Ltd.'s V-260 ^® , V-312 ^® , and V-335 HP ^® are listed. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M ^® -7100, Dong M-8030 ^®, same M-8060 ^®, and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka Yuki Kayaku High School Co., Ltd.'s V-295 ^® , East-300 ^® , East-360 ^® , East-GPT ^® , East-3PA ^® , and East-400 ^® are listed. These products can be used alone or in combination of two or more.

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

The photopolymerizable monomer may be included in an amount of 1% to 20% by weight, such as 1% to 15% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, curing occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, and excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern.

(D) Light polymerization Initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, for example, acetophenone-based compound, benzophenone-based compound, thioxanthone-based compound, benzoin-based compound, triazine-based compound, oxime-based compound, aminoketone-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, 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 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 compound include thioxanthone, 2-methyl thioxanthone, 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, 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-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)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate, etc. are mentioned.

Examples of the aminoketone-based compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1) etc. are mentioned.

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

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

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, for example, 0.3% to 3% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern, and decrease in transmittance due to unreacted initiator Can be prevented.

(F) solvent

Since the photosensitive resin composition according to the embodiment includes quantum dots instead of pigments or dyes as a color material, it may include a solvent having compatibility with the quantum dots, and thus prepared by curing the photosensitive resin composition according to the embodiment It is possible to greatly improve the light conversion rate of the resulting photosensitive resin film.

Solvents having compatibility with the quantum dots include, for example, alkanes (R-H) such as pentane, hexane, and heptane; Aromatic hydrocarbons such as toluene and xylene (Ar-H); Ethers such as diisoamyl ether and dibutyl ether (R-O-R); Alkyl halides (R-X) such as chloroform and trichloromethane; Cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane; (Cyclo)alkyl acetates such as cyclohexyl acetate, pentyl acetate, hexyl acetate, dodecyl acetate, and the like; Ketones such as methyl isobutyl ketone may be used, but are not limited thereto.

The photosensitive resin composition according to the embodiment may further include a solvent having compatibility with the quantum dot as a solvent, as well as a solvent having compatibility with a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a light diffusing agent. However, the binder resin, photopolymerizable monomer, photopolymerization initiator, light diffusing agent, etc. have some degree of compatibility with a solvent having compatibility with the quantum dots, but the quantum dots are the binder resin, photopolymerizable monomer, photopolymerization initiator, and light. Since there is little compatibility with a solvent having compatibility with a diffusing agent, etc., the photosensitive resin composition according to an embodiment may use only a solvent having compatibility with the quantum dots as a solvent, and a solvent having compatibility with the quantum dots And a solvent having compatibility with a binder resin, a photopolymerizable monomer, a photoinitiator, a light diffusing agent, and the like may be mixed and used.

The solvent having compatibility with the binder resin, a photopolymerizable monomer, a photopolymerization initiator, a light diffusing agent, and the like may include alcohols such as methanol and ethanol; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; Acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid Ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like may be used, but are not limited thereto.

For example, the solvent having compatibility with the binder resin, a photopolymerizable monomer, a photopolymerization initiator, etc. may include ketones such as cyclohexanone in consideration of compatibility and reactivity; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; It is preferable to use propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate.

The solvent may be included in the balance based on the total amount of the photosensitive resin composition, for example, 30% to 80% by weight, such as 35% to 80% by weight. When the solvent is included within the above range, since the photosensitive resin composition has an appropriate viscosity, excellent coating properties may be obtained during spin coating and large-area coating using a slit.

(G) Thiol additive

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

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

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

For example, the thiol-based additive may include at least two or more functional groups represented by the following formula (3) at the terminal.

[Formula 3]

In Chemical Formula 3,

L ³ and L ⁴ 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 It is a C2 to C20 heteroarylene group.

For example, the thiol-based additive may be represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

L ³ and L ⁴ 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 Is a C2 to C20 heteroarylene group,

n5 and n6 are each independently an integer of 0 or 1.

For example, in Formulas 3 and 4, L ³ and L ⁴ 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 the following formula (5a), trimethylolpropane tris (3) represented by the following formula (5b). -Mercaptopropionate) (trimethylolpropane tris (3-mercaptopropionate)), pentaerythritol tetrakis (mercaptoacetate) represented by the following formula 5c, Pentaerythritol tetrakis (mercaptoacetate), trimethylolpropane tris represented by the following formula 5d ( 2-mercaptoacetate) (trimethylolpropane tris (2-mercaptoacetate)), glycol di-3-mercaptopropionate represented by the following formula 5e (Glycol di-3-mercaptopropionate) and any selected from the group consisting of a combination thereof There is one.

[Formula 5a]

[Formula 5b]

[Formula 5c]

[Formula 5d]

[Formula 5e]

The thiol-based additive may be included in an amount of 1% to 10% by weight, such as 1% to 5% by weight, based on the total amount of the photosensitive resin composition. When the thiol-based additive is included in an amount of less than 1% by weight, it is difficult to maintain the stability of the quantum dots for each process, and when the thiol-based additive is included in an amount of more than 10% by weight, the patternability of the photosensitive resin composition is deteriorated, and a change with time may occur at room temperature. .

(H) other additives

The photosensitive resin composition according to one embodiment is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; It may further include a fluorine-based surfactant or a combination thereof.

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 the substrate.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-gly Cidoxy 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 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, such as a fluorine-based surfactant, to improve coating properties and prevent defects from being generated, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; ^{Mecha Pack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^®, etc. of Dai Nippon Inki Chemical High School Co., Ltd.; 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 ^{®, ®} -190 copper, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ® , and the like; A fluorine-based surfactant marketed under the names of DIC Corporation's F-482, F-484, F-478, F-554, etc. can be used.

The fluorine-based surfactant may be used in an amount of 0.001 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 ensured, 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 by using the photosensitive resin composition described above.

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

(1) Application and film formation step

The above-described photosensitive resin composition is applied onto a substrate subjected to a predetermined pretreatment to a desired thickness, for example, a thickness of 9 μm to 10 μm using a method such as spin or slit coating, roll coating, screen printing, and applicator method. After application, the coating film is formed by heating at a temperature of about 100° C. for 1 to 10 minutes to remove the solvent.

(2) exposure step

In order to form a pattern required for the obtained coating film, a mask of a predetermined shape is interposed, and then 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. can be used, and in some cases, an X-ray, an electron beam, and the like can 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, for example, 500 mJ/cm ^{2 when using a high-pressure mercury lamp} It is below (by 365 nm sensor).

(3) development stage

Following the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, so that only the exposed portions remain to form an image pattern.

(4) Post-processing 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 development may be cured by heating again or irradiating with actinic rays.

By using the above-described photosensitive resin composition, it is possible to minimize a decrease in the light conversion rate due to the application and coating film formation step, the exposure step, the development step, the post-treatment step, and the like.

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.

(Production of photosensitive resin composition)

Example 1 to Example 7 and Comparative example 1 to Comparative example 7

Photosensitive resin compositions according to Examples 1 to 7 and Comparative Examples 1 to 4 were prepared by using the components mentioned below in the compositions shown in Tables 1 and 2 below.

(1) A photopolymerization initiator is dissolved in a solvent (PGMEA). Here, a photopolymerizable monomer, a binder resin, a thiol-based additive, and a fluorine-based surfactant are added and dissolved sufficiently. Thereafter, the dispersion liquid of the light diffusing agent is added and stirred until evenly dispersed.

(2) A quantum dot powder and a dispersant are dissolved in a solvent (cyclohexyl acetate) and then mixed with a binder resin to prepare a quantum dot-binder resin mixture.

(3) The above-described solution of (1) and the quantum dot-binder resin mixture of (2) were mixed and sufficiently stirred for 30 minutes, and then filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(A) Quantum dots

InP/ZnSe/ZnS quantum dots (fluorescence λ _em =530nm, FWHM=40nm to 60nm, Green QD, Hansol Chemical)

(B) binder resin

SM-400H (SMS company; M _w = 7,000 g/mol)

(The weight average molecular weight of the binder resin was measured by gel permeation chromatography (GPC).)

(C) Photopolymerization Monomer

Dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku company)

(D) Light polymerization Initiator

Oxime initiator (PBG-304, Tronyl company)

(E) light Diffuser

(E-1) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 100 nm, secondary particle diameter: 160 nm, MP414_160, Mikuni)

(E-2) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 100nm, secondary particle diameter: 180nm, MP414_180, Mikuni)

(E-3) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 100nm, secondary particle diameter: 200nm, MP414_200, Mikuni)

(E-4) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 100nm, secondary particle diameter: 240nm, MP414_240, Mikuni)

(E-5) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 80nm, secondary particle diameter: 170nm,, MP386,, Mikuni)

(E-6) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 500nm, secondary particle diameter: 180nm, MP389_240, Mikuni)

(E-7) Anatase type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 150 nm, secondary particle diameter: 170 nm, Aldrich)

(E-8) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 250nm, secondary particle diameter: 230nm, SDT47, Iridos)

(E-9) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 250nm, secondary particle diameter: 210nm, SDT74, Iridos)

(E-10) Rutile type titanium dioxide dispersion (TiO ₂ solid content 20% by weight in PGMEA, primary particle diameter: 170nm, secondary particle diameter: 180nm, SDT74, Iridos)

(F) solvent

(F-1) cyclohexyl acetate

(F-2) Propylene glycol monomethyl ether acetate (PGMEA)

(G) Thiol additive

Glycol di-3-mercaptopropionate (THIOCURE ^® GDMP, BRUNO BOCK)

(H) other additives

Fluorine surfactant (F-554, DIC company)

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 (A) quantum dots 18 18 18 18 18 18 18 (B) binder resin 3 3 3 3 3 3 2.8 (C) photopolymerizable monomer 2 2 2 2 2 2 2 (D) photopolymerization initiator 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (E) light diffusing agent (E-1) 8 - - - - - - (E-2) - 8 - - - - - (E-3) - - 8 - - - 11 (E-4) - - - 8 - - - (E-5) - - - - 8 - - (E-6) - - - - - 8 - (F) solvent (F-1) 30 30 30 30 30 30 28.6 (F-2) 36.5 36.5 36.5 36.5 36.5 36.5 35.1 (G) Thiol-based additive 2 2 2 2 2 2 2 (H) other additives 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Total 100 100 100 100 100 100 100

(Unit: wt%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) quantum dots 18 18 18 18 (B) binder resin 3 3 3 3 (C) photopolymerizable monomer 2 2 2 2 (D) photopolymerization initiator 0.3 0.3 0.3 0.3 (E) light diffusing agent (E-7) 8 - - - (E-8) - 8 - - (E-9) - - 8 - (E-10) - - - 8 (F) solvent (F-1) 30 30 30 30 (F-2) 36.5 36.5 36.5 36.5 (G) Thiol-based additive 2 2 2 2 (H) other additives 0.2 0.2 0.2 0.2 Total 100 100 100 100

Evaluation 1: Blue Light conversion rate And Mineral retention evaluation

Each of the photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 was coated on a glass substrate with a thickness of 6 μm using a spin coater (Mikasa, Opticoat MS-A150, 150 rpm). Then, pre-baking (PRB) at 100° C. for 2 minutes using a hot-plate, and 60 mJ/cm ² to 100 mJ/cm ^{2 using an exposure machine (Ushio, ghi broadband)} After irradiating UV with the power of, post-baking (POB) was performed at 180° C. for 30 minutes in a convection clean oven (jongro), and the blue light conversion rate was measured.

In the post-baking step, the light absorption rate and light conversion rate of blue light incident from the BLU to green were evaluated, and the results are shown in Table 3 below. Here, the measurement of the blue light conversion rate was measured with Otsuka's QE-5000 equipment, and the bare glass was placed on the blue BLU covered with the diffusing film and measured with a detector. The single film coated with the photosensitive resin composition according to Comparative Examples 1 to 4 was placed, and the increase in the peak converted to green compared to the decrease in the blue light absorption peak was calculated, and the light conversion rate (Green/Blue) was measured.

Evaluation 2: sedimentation evaluation

20 ml of the photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were left at room temperature for 6 days.

Sedimentation occurs naturally depending on the physical density of TiO _{2. Ref.} The degree of sedimentation compared to (Comparative Example 3) was expressed as %.

Blue light conversion rate (after POB) (%) Sedimentation degree (compared to Ref, %) Remark Example 1 23.3 -49% Surface uniformity after development Example 2 23.9 -50% Surface uniformity after development Example 3 24.4 -46% Surface uniformity after development Example 4 24.5 -48% Surface unevenness after development Example 5 23.9 -62% Surface uniformity after development Example 6 21.8 -75% Surface uniformity after development Example 7 25.4 -47% Surface uniformity after development Comparative Example 1 22.8 -40% Surface uniformity after development Comparative Example 2 25.6 +30% Surface unevenness after development Comparative Example 3 25.4 Ref Surface unevenness after development Comparative Example 4 25.6 -27% Surface uniformity after development

Referring to Table 3, when controlling the primary and secondary particle diameters of the light diffusing agent to 80 nm to 200 nm and 120 nm to 250 nm, respectively, a light diffusing agent having no primary and secondary particle diameters in the above range is used. It can be seen that the sedimentation degree is improved than that of the case. Furthermore, if the primary or secondary particle diameter of the light diffusing agent exceeds a specific particle diameter, the surface non-uniform phenomenon of the coating film after development occurs. It can also be confirmed that there is a need. In addition, the product containing particles in the above range but whose crystal phase is Anatase (Comparative Example 1) was excellent in sedimentation characteristics, but low light conversion rate. And, as in Example 7, the content of the dispersion was increased to maximize the improvement of the sedimentation degree while maintaining the optical characteristics similar to those of Comparative Example 3.

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

Claims (11)

(A) quantum dots;
(B) binder resin;
(C) photopolymerizable monomer;
(D) photoinitiator;
(E) light diffusing agent; And
(F) solvent
Including,
The light diffusing agent has a primary particle diameter of 80 nm to 120 nm, a secondary particle diameter of 160 nm to 230 nm,
The light diffusing agent is a rutile type titanium dioxide photosensitive resin composition.
delete delete delete The method of claim 1,
The quantum dots are 450nm to 580nm at the maximum fluorescence wavelength (fluorescence λ _em) having a quantum dot, the quantum dot from 580nm to 700nm with a maximum fluorescence wavelength (fluorescence λ _em) or a photosensitive resin composition comprising a combination of the two.
The method of claim 1,
The photosensitive resin composition further comprises (G) a thiol-based additive.
The method of claim 6,
The thiol-based additive is a photosensitive resin composition containing 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition
The (A) quantum dots 1% to 30% by weight;
(B) 1% to 20% by weight of the binder resin;
1% to 20% by weight of the (C) photopolymerizable monomer;
(D) 0.1% to 5% by weight of the photopolymerization initiator;
(E) 5% to 15% by weight of the light diffusing agent; And
30% to 80% by weight of the solvent (F)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; A photosensitive resin composition further comprising a fluorine-based surfactant or a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 and 5 to 9.
A color filter comprising the photosensitive resin film of claim 10.

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