KR20190139029A - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising: (A) quantum dots; (B) a binder resin; (C) a polymerizable monomer; (D) a photopolymerization initiator; (E) a light diffusing agent; (F) a resin including a structural unit represented by chemical formula 1; and (G) a solvent, to a photosensitive resin film manufactured using the same, and to a color filter comprising the photosensitive resin film. In the chemical formula 1, each substituent is the same as defined in the specification.

Description

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

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

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

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

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

Accordingly, quantum dot-containing photosensitive resin compositions that can significantly improve the reliability of chemical resistance, heat resistance, and the like by using quantum dots instead of conventional color materials such as dyes or pigments have recently attracted attention.

In the case of the conventional quantum dot-containing photosensitive resin composition, a light diffusing agent such as titanium dioxide, which is a dispersion, is used in order to increase the absorption characteristic. When titanium dioxide is used, precipitation problems occur in the quantum dot-containing photosensitive resin composition due to the particle size of titanium dioxide. When such precipitation occurs, it is difficult to secure uniformity of the entire composition including the upper and lower compositions, and such non-uniformity makes it difficult to ensure the light absorption of the quantum dot-containing photosensitive resin composition, and ultimately affects the overall composition.

In order to solve the problem of light diffusion agent precipitation such as titanium dioxide, the present inventors modify the cellulose resin in the composition to form a hydrogen bond type framework with titanium dioxide, thereby solving the problem of light diffusion agent precipitation such as titanium dioxide. Was intended.

One embodiment is to provide a quantum dot-containing photosensitive resin composition, excellent in viscosity, light absorption, 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) quantum dots; (B) binder resin; (C) a polymerizable monomer; (D) photoinitiator; (E) light diffusing agents; (F) Resin comprising a structural unit represented by the following formula (1); And (G) provides a photosensitive resin composition comprising a solvent.

[Formula 1]

In Chemical Formula 1,

R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,

s is an integer from 2 to 100.

Resin including the structural unit represented by the formula (1) may be represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,

R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom or a sulfone group, provided that at least one of R ³ and R ⁴ is a sulfone group,

s is an integer from 2 to 100.

R ³⁰³ and R ³⁰⁴ may each independently be a sulfone group.

S may be an integer of 2 to 20.

The resin including the structural unit represented by Formula 1 may be included in an amount of 2% by weight 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 a cardo-based binder resin, an acrylic binder resin, or a combination thereof.

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

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

The photosensitive resin composition may include 1 wt% to 40 wt% of the (A) quantum dots based on the total weight of the photosensitive resin composition; 1 wt% to 30 wt% of the (B) binder resin; 0.5% to 20% by weight of the polymerizable monomer (C); 0.1 wt% to 10 wt% of the (D) photopolymerization initiator; 0.1% to 20% by weight of the light diffusing agent (E); 1 to 5% by weight of a resin containing the structural unit represented by Formula (F) 1; And (G) 20 wt% to 80 wt% of the solvent.

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

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

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

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

The modified cellulose resin can be used to form a hydrogen bond type framework with the light diffusing agent in the photosensitive resin composition, thereby preventing precipitation of the light diffusing agent, and ultimately providing a photosensitive resin composition having excellent storage stability and the like.

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

Unless stated otherwise in the present specification, "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, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" Is a C1 to C20 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and "alkylarylene group" refers to a C6 to C20 alkylarylene group, and a "heteroarylene group" to C3 to C20 hetero It means an arylene group and a "alkoxy group" means a C1-C20 alkoxylene group.

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

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

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

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

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

In the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Chemical Formulas 3-1 to 3-11 is included in the backbone of the resin.

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

Photosensitive resin composition according to one embodiment is (A) quantum dots; (B) binder resin; (C) a polymerizable monomer; (D) photoinitiator; (E) light diffusing agents; (F) Resin comprising a structural unit represented by the following formula (1); And (G) a solvent.

[Formula 1]

In Chemical Formula 1,

R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,

s is an integer from 2 to 100.

The color filter using the photosensitive resin composition can be manufactured by coating three or more colors on a transparent substrate mainly by dyeing, electrodeposition, printing, pigment dispersion, etc. In recent years, pigment dispersion technology has been improved, resulting in excellent color reproducibility and The pigment dispersion method which ensures durability to heat, light, and humidity is mainly used. The color filter using the pigment dispersion method implements high brightness and high contrast ratio using pigment miniaturization and surface treatment, or recently, the development of a high-performance color filter applying a dye. In addition, various types of substrates are required for flexible display, and in particular, it is necessary to develop a color filter that satisfies limited process conditions in order to manufacture a color filter in an organic plastic substrate.

Recently, photosensitive resin compositions using quantum dots instead of conventional dyes or pigments have been attracting much attention as colorants. However, quantum dots are more unstable than dyes or pigments, and when the photosensitive resin composition containing quantum dots is left at a high temperature for a long time, the viscosity change of the composition becomes large, resulting in a decrease in storage stability, thereby resulting in a problem in that light absorption is also lowered.

According to one embodiment, the quantum dot-containing photosensitive resin composition may significantly improve storage stability and light absorption of the quantum dot-containing photosensitive resin composition by using a resin including a modified cellulose structural unit. Furthermore, the residual film rate and chemical resistance may also be improved. Can be improved.

In addition, the photosensitive resin composition according to an embodiment may be used by mixing three different compounds ((meth) acrylate-based compound, oxetane-based compound and thiol group-containing compound) as the polymerizable monomer, with the sulfonium-based cation Since the initiator may be further included, excellent resolution and durability may be ensured only by the low temperature curing process.

Furthermore, the photosensitive resin composition according to the embodiment may further include a curing accelerator, wherein the curing accelerator promotes the thermosetting reaction of the photosensitive resin composition, thereby preventing the invasion of the pattern that may occur during the development process to implement a high resolution micropattern. This is possible. In addition, the flow of the pattern that can occur in the post-baking process is prevented to maintain the taper angle relatively high, and the cohesion within the pattern is improved to increase the adhesion of the pattern.

Each component is demonstrated concretely below.

(F) Resin comprising a structural unit represented by formula (1)

The photosensitive resin composition according to one embodiment includes a structural unit represented by Chemical Formula 1, that is, a modified cellulose resin.

The structural unit represented by Chemical Formula 1, that is, the structure of the modified cellulose resin is different from the general cellulose resin, in that it has a * -CHNH functional group instead of a * -CH ₂ OH functional group. Both the OH group and the NH group are functional groups capable of hydrogen bonding, but since the NH group has stronger hydrogen bonding force than the OH group, when using a resin containing the structural unit represented by Formula 1 above general cellulose resin, The hydrogen bond framework with the light diffusing agent mentioned later can be formed well. That is, the precipitation of the light diffusing agent can be effectively prevented even in a small amount. In addition, when using a relatively large amount of the general cellulose resin, it is possible to prevent the precipitation of the light diffusing agent, but there is a problem that other physical properties such as chemical resistance or residual film rate is lowered, according to one embodiment, a small amount Since the modified cellulose resin is used, the fall of physical properties, such as chemical resistance and residual film rate, can be prevented with the precipitation prevention of a light-diffusion agent.

For example, the resin including the structural unit represented by Chemical Formula 1 may be represented by the following Chemical Formula 2.

[Formula 2]

In Chemical Formula 2,

R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,

R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom or a sulfone group, provided that at least one of R ³ and R ⁴ is a sulfone group,

s is an integer from 2 to 100.

For example, R ³⁰³ and R ³⁰⁴ may each independently be a sulfone group.

The structure of the resin represented by Chemical Formula 2, that is, the modified cellulose resin is different from that of a general cellulose resin, in that a sulfone group is necessarily present at at least one of both terminals. Since the sulfone groups present at the terminals are well soluble in a solvent such as propylene glycol monomethyl ether acetate as well as water, the modified cellulose resin represented by Formula 2 may have excellent solubility (dispersibility) in the solvents described below. .

For example, the s may be an integer of 2 to 20.

For example, in Formula 2, when R ³⁰¹ and R ³⁰² are each independently a hydroxyl group, and R ³⁰³ and R ³⁰⁴ are each independently a sulfone group, the resin represented by Formula 2 is hydrogen-bonded with a light diffusing agent to be described later, It may have a structure represented by the formula (E-1).

[Formula E-1]

Due to the hydrogen bonding force between the modified cellulose resin and the light diffusing agent (titanium dioxide), precipitation of titanium dioxide is prevented, thereby ultimately having excellent storage stability and light absorption rate even at high temperature.

Resin including the structural unit represented by the formula (1) may be included in 1% to 5% by weight, such as 2% to 4% by weight based on the total amount of the photosensitive resin composition. When the modified cellulose resin is included in the above range, it is possible to sufficiently prevent the precipitation of the light diffusing agent by hydrogen bonding with the light diffusing agent, and the solubility in the solvent is further improved to obtain excellent storage stability and dispersibility. have.

(A) quantum dots

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

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

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

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

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

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

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

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

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

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

(B) binder resin

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

When the binder resin contains a cardo-based binder resin, the developability of the photosensitive resin composition is excellent, and the sensitivity at the time of photocuring is good, and thus the fine pattern formability 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 , wherein R ¹⁰⁷ to R ¹¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, or Any one of the linking groups represented by Formulas 3-1 to 3-11,

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

(In Chemical 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 dianhydride 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 in manufacturing the light shielding layer, and 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 Formula 4 at at least one of both ends.

[Formula 4]

In Chemical Formula 4,

Z ³ may be represented by the following Chemical 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, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group or C2 to C20 alkenylamine group.)

[Formula 4-6]

[Formula 4-7]

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

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 C1-10 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 may include a structural unit represented by Chemical Formulas 5-1 to 5-5 to secure high heat resistance and high brightness while controlling developability of a pattern, and when used with the cardo-based resin, It is possible to implement a fine pattern by increasing the adhesion of the pattern, has a high resolution, and can also secure a high transmittance.

The epoxy binder resin may include a phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or a combination thereof, but is not limited thereto.

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

[Formula 6]

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

(C) polymerizable monomer

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

For example, the polymerizable monomer may be a (meth) acrylate-based compound (photopolymerizable monomer) represented by the following formula (7), an oxetane-based compound (thermally polymerizable monomer) 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 degree of curing during photocuring and thermosetting.

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

In addition, the thiol group-containing compound represented by the formula (9) is located in the middle of the thiol group is not the compound terminal, it can solve the problem of odor generated during the color filter process.

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

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

The polymerizable monomer may be included in an amount of 0.5 wt% to 20 wt%, such as 1 wt% to 15 wt%, based on the total amount of the photosensitive resin composition. When the polymerizable monomer is included in the above range, curing is sufficiently performed upon exposure in the pattern forming process, and thus the reliability is excellent, and heat resistance, light resistance, chemical resistance, resolution, and adhesion of the pattern are also excellent.

(D) photoinitiator

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

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

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

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

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

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

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

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

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

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

The photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, such as 0.5 wt% to 5 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, it is excellent in the sensitivity and developability balance during exposure to obtain a pattern having excellent resolution without a residual film.

(E) light diffusing agent

On the other hand, the photosensitive resin composition further includes a light diffusing agent.

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.

The light diffusing agent reflects light that is not absorbed by the quantum dots, 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 150nm to 250nm, specifically 180nm to 230nm. When the average particle diameter of the light diffusing agent is in the above range, it may have a more excellent light diffusion effect, it is possible to increase the light conversion efficiency.

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

(G) solvent

The solvent may have a 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 do not react.

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 monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol 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; Oxy acetic acid alkyl esters such as methyl oxy acetate, oxy ethyl acetate and oxy butyl acetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxy propionic acid alkyl esters such as methyl 3-oxy propionate and ethyl 3-oxypropionate; 3-alkoxy propionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate and 3-ethoxy methyl propionate; 2-oxy propionic acid alkyl esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate and 2-oxy propionic acid propyl; 2-alkoxy propionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate and 2-ethoxy methyl propionate; 2-oxy-2-methyl propionic acid esters, such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of 2-alkoxy-2-methyl propionic acid alkyls such as methyl methyl propionate; Esters such as ethyl 2-hydroxy propionate, ethyl 2-hydroxy-2-methyl propionate, ethyl hydroxy acetate, and methyl 2-hydroxy-3-methyl butanoate; Ketone acid esters such as ethyl pyruvate and the like, and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents, such as ethyl, diethyl oxalate, diethyl maleate, (gamma) butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, are mentioned.

Among them, 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 2-hydroxy ethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

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

(H) Thermal polymerization initiator

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

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

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

The sulfonium-based cation initiator may be used to have an endothermic peak at a temperature at the time of the post-baking process, such as less than 200 ℃, such as 100 ℃ to 170 ℃ measured by the 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 200 ° C or higher, which is similar to or higher than the thermosetting temperature of the photosensitive resin composition. In addition, the sulfonium-based cationic initiator may not play a role in polymerizing the binder resin, for example, the epoxy resin and / or the acrylic resin in the binder resin, before heat curing of the photosensitive resin composition, or the reaction rate may be too slow. As a result, the epoxy-based resin is polymerized during curing of the photosensitive resin composition, thereby preventing the holding of the photosensitive resin film and the like, and thus failing to achieve the above object.

The sulfonium-based cation initiator may include, for example, a compound represented by the following Formula 10.

[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 Ring C2 to C20 heteroaryl group or a combination thereof,

m is an integer from 0 to 6,

n is an integer of 0-5.

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

Scheme 1

Scheme 2

Scheme 3

In 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 mole number of the epoxy-based binder resin participating in the reaction, and m is an integer of 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 between a polymerizable monomer and a binder resin, such as an epoxy resin and / or an acrylic resin in the binder resin, such as a thermosetting reaction.

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 less than 0.1% by weight of the total amount of the photosensitive resin composition, the curing speed is slowed, so that the resolution of the pattern is poor, and taper angle cannot be formed high, and the curing accelerator is 3% by weight of the total amount of the photosensitive resin composition. When it is contained in more than%, the curing rate is faster than necessary, not only deterioration of the straightness due to excessive melting characteristics deterioration during the post-baking process, but also the adhesion strength is also reduced.

The curing accelerator may be an imidazole-based curing accelerator, the imidazole-based curing accelerator may be represented by the following formula (11).

[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

Photosensitive resin composition according to one embodiment is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Or a combination thereof.

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

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ isocyanate propyl triethoxysilane, and γ glycidoxy propyl. Trimethoxysilane, (beta) epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

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

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

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like from BM Chemie Co .; Mecha packs F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Co., Ltd .; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Grass Co., Ltd .; Toray Silicone ^® (Note)社SH-28PA, 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 an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, coating uniformity is secured, staining does not occur, and wetting on the glass substrate is excellent.

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

The above-mentioned photosensitive resin composition is coated on a substrate subjected to a predetermined pretreatment to a desired thickness using a method such as spin or slit coating, roll coating, screen printing, applicator, or the like, for example, a thickness of 1.2 µm to 3.5 µm. After coating, the coating is formed by heating at a temperature of 70 ° C to 90 ° C for 1 to 10 minutes to remove the solvent.

(2) exposure step

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

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

(3) developing stage

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

(4) post-processing steps

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

By using the above-mentioned photosensitive resin composition, 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 are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

(Example)

(Modified cellulose resin production)

1,3-Propanesultone was added to the Hydroxyl end of the Microcrystalline Cellulose in THF solvent at a temperature of 50 ° C. to obtain an intermediate product through a sulfonation reaction. The intermediate product was reacted with Amino terminated polyethylene oxide at a temperature of 70 ° C. to prepare a modified cellulose resin represented by the following formula S-1.

[Formula S-1]

(Photosensitive resin composition production)

Examples 1 to 5 and Comparative Examples 1 to 3

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

Specifically, after dissolving a photopolymerization initiator, a thermal polymerization initiator, a binder resin, a curing accelerator and / or a thermosetting initiator in a solvent, and stirred at room temperature for about 2 hours. Then, an acrylic binder resin, a modified or unmodified cellulose resin, a quantum dot, a light diffusing agent and a polymerizable monomer were added and stirred at room temperature for 2 hours. After adding the additive 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) colorant

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

(B) binder resin

  (B-1) cardo resin (V259ME, NIPPON STEEL)

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

(C) polymerizable monomer

  (C-1) Photopolymerizable Monomer: dipentaerythritol hexaacrylate (Japanese Pharmaceutics Co., Ltd., DPHA)

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

  (C-3) Thermally polymerizable monomer: Oxetane-based compound (Toagosei, OXT-212)

(D) photoinitiator

  (D-1) OXE01 (BASF Corporation)

  (D-2) IRG369 (BASFf)

(E) light diffusing agent

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

(F) cellulose resin

  (F-1) Modified cellulose resin (indicated by Chemical Formula S-1)

  (F-2) Unmodified Cellulose Resin (Aldrich, Microcrystalline Cellulose)

(G) solvent

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

(H) Thermal polymerization initiator

  TA-100 (San-Apro)

(I) curing accelerator

  Imidazole series curing accelerator (2-methyl imidazole) (Shikoku, Curezol 2MZ)

(J) other additives

  Leveling agent (DIC, F-554)

(Unit: weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) quantum dots 53.000 53.000 53.000 53.000 53.000 53.000 53.000 53.000 (B) binder resin (B-1) 1.179 1.179 1.179 1.179 1.179 5.679 1.179 1.179 (B-2) 3.249 3.249 3.249 3.249 3.249 3.249 7.749 3.249 (C) polymerizable monomer (C-1) 1.180 1.180 1.180 1.180 1.180 1.180 1.180 1.180 (C-2) 0.393 0.393 0.393 0.393 0.393 0.393 0.393 0.393 (C-3) 0.393 0.393 0.393 0.393 0.393 0.393 0.393 0.393 (D) photoinitiator (D-1) 0.101 0.101 0.101 0.101 0.101 0.101 0.101 0.101 (D-2) 1.038 1.038 1.038 1.038 1.038 1.038 1.038 1.038 (E) light diffusing agent 6.750 10.750 6.750 6.750 6.750 6.750 6.750 6.750 (F) cellulose resin (F-1) 3.000 3.000 1.000 5.000 3.000 - - - (F-2) - - - - - - - 3.000 (G) solvent 28.095 25.595 31.595 27.595 29.595 28.095 28.095 29.595 (H) Thermal polymerization initiator 0.022 0.022 0.022 0.022 0.022 0.022 0.022 0.022 (I) curing accelerator 1.500 - - - - - - - (H) other additives 0.100 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Sum 100.0 100.0 100.0 100.0 100. 100.0 100.000 100.0

Evaluation 1: Viscosity Evaluation

For each of the photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 using a viscometer (Brookfield's DV-II, RV-2 spindle, 23rpm) for each storage period (45 ℃, humidity conditions) The viscosity value was measured, and the results are shown in Table 2 below.

(Unit: cP (mPas)) Save
term Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 days 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 2 days 4.5 4.7 4.5 4.5 4.5 4.6 5.2   5.0 7 days 4.5 4.7 4.6 4.5 4.5 5.7 6.8 6.5 15th 4.5 4.7 4.7 4.5 4.5 6.9 8.8 9.2 30 days 4.5 4.7 4.8 4.5 4.5 10.1 12.2 10.8

Evaluation 2: evaluation of light absorption

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

(unit: %) storage duration Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 days 88.12 94.34 94.32 94.12 88.10 88.02 88.34 88.42 2 days 88.12 94.34 94.30 94.11 88.11 88.01 88.30 88.42 7 days 88.22 94.35 94.10 94.12 88.11 87.58 87.44 87.77 15th 88.21 94.34 93.62 94.12 88.10 86.43 86.33 87.22 30 days 88.21 94.33 93.03 94.12 88.12 86.01 85.87 86.22

Evaluation 3: Residual Rate Evaluation

The photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were coated on a glass substrate by using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, respectively, and then hot plates (hot -plate) was soft-baked at 80 ° C. for 120 seconds and exposed to a power of 60 mJ using an exposure machine (Ughio, ghi broadband). Subsequently, it was developed with 0.2 wt% of potassium hydroxide (KOH) aqueous solution using a developer (SVS, SSP-200). Thereafter, hard-baking was performed at 100 ° C., 150 ° C., and 200 ° C. for 30 minutes in the convection oven, and further cured at 200 ° C. for 30 minutes. The remaining film ratio was calculated by measuring the height of the pattern after the hard-baking and the additional curing for each coating, exposure, development, and temperature for each storage period (at room temperature (25 ° C.) and humidity conditions), and the results are as follows. Table 4 shows.

Residual Rate Evaluation Criteria

○: less than 3% residual film

△: less than 5% residual film

X: 5% excess film reduction

Save
term Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 days ○ ○ ○ ○ ○ ○ ○ ○ 2 days ○ ○ ○ ○ ○ ○ ○ ○ 7 days ○ ○ △ ○ ○ X X △ 15th ○ ○ △ ○ ○ X X X 30 days ○ ○ X ○ ○ X X X

Evaluation 4: chemical resistance evaluation

The photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 3 were coated on a glass substrate by using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 3 μm, respectively, and then hot plates (hot -plate) was soft-baked at 80 ° C. for 120 seconds and exposed to a power of 60 mJ using an exposure machine (Ughio, ghi broadband). Subsequently, it was developed with 0.2 wt% of potassium hydroxide (KOH) aqueous 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, respectively, 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, but was evaluated for each storage period (at room temperature (25 ° C.) and moisture-free conditions), and the results are shown in Table 5 below.

The chemical resistance was evaluated by color change (ΔEab *) of the coating film before and after immersion in NMP solvent, and the color change (ΔEab *) was measured using a spectrophotometer (Otsuka Electronics, MCPD3000).

Chemical Resistance Evaluation Criteria

○: ΔEab * is 3% or less

Δ: ΔEab * is 5% or less

Ⅹ: ΔEab *> 5%

Save
term Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 days ○ ○ ○ ○ ○ ○ ○ ○ 2 days ○ ○ ○ ○ ○ ○ ○ △ 7 days ○ ○ △ ○ ○ △ Ⅹ Ⅹ 15th ○ ○ △ ○ ○ △ Ⅹ Ⅹ 30 days ○ ○ △ ○ ○ Ⅹ Ⅹ Ⅹ

As shown in Table 2, the photosensitive resin composition (Examples 1 to 5) according to the embodiment was maintained without changing the viscosity for a long time at a high temperature of 45 ℃ than the photosensitive resin composition of Comparative Examples 1 to 3, It can be seen that even when the imidazole additive for cure acceleration is included, it shows a stable viscosity value.

As shown in Table 3, the photosensitive resin composition (Examples 1 to 5) according to the embodiment is maintained for a longer time than the photosensitive resin composition of Comparative Examples 1 to 3, the titanium dioxide is It can be seen that the initial value is maintained even if it is included in excess.

As shown in Table 4, the photosensitive resin composition (Examples 1 to 5) according to one embodiment has a uniform residual film reduction even after long-term storage, but the photosensitive resin composition of Comparative Examples 1 to 3 after 7 days It can be seen that residual film imbalance occurs.

As shown in Table 4, in the case of the photosensitive resin composition (Examples 1 to 5) according to one embodiment, ΔEab * is uniform at 3% or less, but the photosensitive resin composition of Comparative Examples 1 to 3 is long-term. You can see the color change after saving.

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

Claims (12)

(A) quantum dots;
(B) binder resin;
(C) a polymerizable monomer;
(D) photoinitiator;
(E) light diffusing agents;
(F) Resin comprising a structural unit represented by the following formula (1); And
(G) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Chemical Formula 1,
R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,
s is an integer from 2 to 100.
The method of claim 1,
Resin comprising a structural unit represented by the formula (1) is a photosensitive resin composition represented by the formula (2):
[Formula 2]

In Chemical Formula 2,
R ³⁰¹ and R ³⁰² are each independently an amine group, a hydroxyl group, a fluorine group, or a combination thereof,
R ³⁰³ and R ³⁰⁴ are each independently a hydrogen atom or a sulfone group, provided that at least one of R ³ and R ⁴ is a sulfone group,
s is an integer from 2 to 100.
The method of claim 1,
Said R ³⁰³ and R ³⁰⁴ are each independently a sulfone group.
The method of claim 1,
Resin comprising a structural unit represented by the formula (1) is 1% by weight to 5% by weight relative to the total amount of the photosensitive resin composition.
The method of claim 1,
The light diffusing agent is titanium dioxide photosensitive resin composition.
The method of claim 1,
The binder resin is a photosensitive resin composition comprising a cardo-based binder resin, an acrylic binder resin or a combination thereof.
The method of claim 1,
The said polymerizable monomer is a photosensitive resin composition containing a (meth) acrylate type compound, an oxetane type compound, a thiol group containing compound, or a combination thereof.
The method of claim 1,
The photosensitive resin composition further comprises a thermal polymerization initiator, a curing accelerator or a combination thereof.
The method of claim 1,
The photosensitive resin composition is based on the total weight of the photosensitive resin composition,
(A) 1 wt% to 40 wt% of the quantum dots;
1 wt% to 30 wt% of the (B) binder resin;
0.5% to 20% by weight of the polymerizable monomer (C);
0.1 wt% to 10 wt% of the (D) photopolymerization initiator;
0.1% to 20% by weight of the light diffusing agent (E);
1 weight% to 5 weight% of a resin including the structural unit represented by Formula (F) 1; And
20% to 80% by weight of the solvent (G)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Or a combination thereof.
The photosensitive resin film manufactured using the photosensitive resin composition of any one of Claims 1-10.
The color filter containing the photosensitive resin film of Claim 11.