KR101869392B1

KR101869392B1 - Photosensitive resin composition, photosensitive organic layerusing the same and color filter

Info

Publication number: KR101869392B1
Application number: KR1020150164815A
Authority: KR
Inventors: 권지윤; 강용희; 권오범; 박상천; 백호정; 조성서
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-11-24
Filing date: 2015-11-24
Publication date: 2018-06-20
Also published as: KR20170060400A

Abstract

(A) a photo-conversion material; (B) a binder resin; (C) a photopolymerizable monomer comprising at least two functional groups represented by the following formula (1); (D) a photopolymerization initiator; And (E) a solvent, a photosensitive organic film prepared using the same, and a color filter comprising the organic film.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive organic film, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a photosensitive organic film produced using the same, and a color filter comprising the photosensitive organic film.

Generally, a color filter applied to a display forms a desired pattern through an exposure process using a photoresist composition using a photosensitive resist composition, and forms a color filter through a patterning process in which an unexposed portion is dissolved and removed through a development process. The material for the color filter is alkali-soluble and requires high sensitivity, adhesion to the substrate, chemical resistance, and heat resistance. However, since the curing reaction is usually insufficient by the exposure process alone, a step of thermally curing at a high temperature of 200 ° C or more is required for obtaining the required properties. Therefore, there are limitations in applications requiring low-temperature processes such as electronic paper and OLED.

On the other hand, in order to develop a photosensitive resin composition for a color filter which requires application of a relatively low temperature process such as electronic paper and OLED, there has been an effort to supplement the poor curing characteristics by adding additional compounds such as epoxide and peroxide, There is a problem that reliability is low.

The above problem is caused by the fact that the coloring material such as pigment or dye competitively absorbs the photopolymerization initiator and the light energy, and since it acts to remove the radicals generated by the pigment and the dye, it is difficult to obtain sufficient initiation efficiency, The curing rate of the synthetic monomer is reduced compared with the case where the coloring material is not used.

Therefore, efforts have been made to develop a low-temperature curing photosensitive resin composition which can remarkably improve reliability such as chemical resistance, heat resistance and the like by using other materials instead of color materials such as existing dyes or pigments.

One embodiment is to provide a photosensitive resin composition having excellent reliability such as chemical resistance and heat resistance even under a low-temperature curing process.

Another embodiment is to provide a photosensitive organic film excellent in photo-conversion efficiency, which is produced by using the photosensitive resin composition.

Another embodiment is to provide a color filter comprising the photosensitive organic film.

One embodiment includes (A) a photo-conversion material; (B) a binder resin; (C) a photopolymerizable monomer comprising at least two functional groups represented by the following formula (1); (D) a photopolymerization initiator; And (E) a solvent.

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

The photopolymerizable monomer may contain 2 to 6 functional groups represented by the formula (1).

The photopolymerizable monomer may include a linking group represented by the following general formulas (2) and (3).

(2)

(3)

In Formula 3,

L ² is a substituted or unsubstituted C1 to C10 alkylene group.

The photopolymerizable monomer may include a linking group represented by the following general formula (4).

[Chemical Formula 4]

In Formula 4,

L ³ to L ⁶ are each independently a substituted or unsubstituted C1 to C10 alkylene group,

m and n are each independently an integer of 1 to 10;

The photopolymerizable monomer may include a compound represented by the following formula (5), a compound represented by the following formula (6), or a combination thereof.

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)

p, q, r and s are each independently an integer of 1 to 10;

The photopolymerizable monomer may contain the compound represented by Formula 5 and the compound represented by Formula 6 at a weight ratio of 3: 7 to 7: 3.

The photosensitive resin composition may further comprise (F) a diffusing agent.

The diffusing agent may comprise barium sulphate, calcium carbonate, titanium dioxide or a combination thereof.

The diffusing agent may be included in an amount of 1 wt% to 5 wt% based on the total amount of the photosensitive resin composition.

The diffusing agent may have an average particle diameter of 150 nm to 250 nm.

The photo-conversion material may absorb light in a wavelength range of 360 nm to 780 nm and emit fluorescence in a wavelength range of 580 nm to 700 nm.

The photo-conversion material may be a quantum dot.

The photosensitive resin composition may further comprise 1 to 30% by weight of the photoconversion material (A) relative to the total amount of the photosensitive resin composition; 5 to 30% by weight of the binder resin (B); 1 to 20% by weight of the (C) photopolymerizable monomer; 0.1 to 5% by weight of the photopolymerization initiator (D); And (E) the solvent balance.

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

Another embodiment provides a photosensitive organic film produced using the photosensitive resin composition.

Another embodiment provides a color filter comprising the photosensitive organic film.

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

A photosensitive resin composition excellent in reliability such as chemical resistance and heat resistance can be provided even in a low temperature curing process and a photosensitive organic film prepared using the photosensitive resin composition containing a photoconversion material has excellent light conversion efficiency and is useful for color filters and the like Lt; / RTI >

FIG. 1 shows the absorption / emission spectra of the photo-conversion material (quantum dots) used in Examples 1 to 5 and Comparative Examples 1 to 4. FIG.
2 is a pattern photograph of a photosensitive organic film (QD film) produced using the photosensitive resin composition (QD PR) according to Comparative Example 1 in a high-temperature (230 ° C) process.
3 to 6 are pattern photographs of the photosensitive organic film (QD film) produced using the photosensitive resin composition (QD PR) according to Comparative Examples 1 to 4 in a low temperature (150 ° C) process independently.
7 to 11 are pattern photographs of the photosensitive organic film (QD film) produced using the photosensitive resin composition (QD PR) according to Examples 1 to 5 in the low temperature (150 ° C) process independently of each other.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

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

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (7-1) to (7-11) is contained in the main backbone of the resin.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (A) a photo-conversion material; (B) a binder resin; (C) a photopolymerizable monomer containing at least two functional groups represented by the following formula (1) at the terminal thereof; (D) a photopolymerization initiator; And (E) a solvent.

Each component will be described in detail below.

(A) Photoconversion material

As shown in FIG. 1, the photoconversion material according to the present invention absorbs light in a wavelength range of 360 nm to 780 nm, for example, a wavelength range of 400 nm to 780 nm, and emits fluorescence in a wavelength range of 580 nm to 700 nm, Can be released. That is, the light conversion material may have a maximum fluorescence wavelength (fluorescence λ _em) at 600nm to 650nm.

In addition, the absolute quantum efficiency (PLQY) of the photo-conversion material may have a light conversion efficiency of 20% or more, for example, 40% or more.

For example, the photo-conversion material may be a quantum dot.

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

The quantum dot may be an organic material or an inorganic material or a hybrid of an organic material and an inorganic material.

The quantum dot may comprise a core and a shell surrounding the core. The core and the shell may each independently comprise a core, a core / shell, a core / a first shell / a second shell, , Alloys, alloys / shells, and the like, but the present invention is not limited thereto.

For example, the core may include at least one material selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InAs and alloys thereof , But is not 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.

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

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

In order to improve the stability and dispersibility of the quantum dots, the organic material may be stabilized by substituting organic materials on the surface of the shell. The organic materials may include thiol, amine, phosphine oxide, acryl, Si, But is not limited thereto.

FIG. 1 is an absorption and emission spectrum of InP / ZnS core / shell type quantum dots (fluorescence λem = 630 nm, FWHM = 45 nm) included in the photosensitive resin composition according to one embodiment. In one embodiment, in recent years, interest in the environment has greatly increased worldwide and regulations on toxic substances have been strengthened, so that instead of a luminescent substance having a cadmium-based core, quantum yield is somewhat low but environmentally friendly A non-cadmium-based light emitting material is used, but the present invention is not limited thereto.

The photoconversion material may be included in an amount of 1% by weight to 30% by weight, for example, 10% by weight to 20% by weight based on the total amount of the photosensitive resin composition according to one embodiment. When the photo-conversion material is included within the above range, the photo-conversion characteristic inherent to the photo-conversion material can be prevented and the photo-conversion efficiency can be prevented from being reduced.

(B) binder resin

The binder resin according to the present invention may include an acrylic binder resin, a cadmium 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 with the first ethylenically unsaturated monomer, and may be a resin containing at least one acrylic repeating unit.

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

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight to 40% by weight based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl 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; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly 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, and (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but not limited thereto, Or more may be used in combination.

The weight average molecular weight of the acrylic binder resin may be from 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, it has good adhesion with the substrate, good physical and chemical properties, and good viscosity.

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 cadmium-based binder resin may include a repeating unit represented by the following general formula (7).

(7)

In Formula 7,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxy 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) Is any one of the linking groups represented by formulas (7-1) to (7-11)

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Chemical Formula 7-4]

[Formula 7-5]

(7-5)

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 7-6]

[Formula 7-7]

[Formula 7-8]

[Formula 7-9]

[Formula 7-10]

[Formula 7-11]

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 cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, pattern formation is good without residue during the production of the photosensitive organic film, no loss of film thickness during development, and good patterns can be obtained.

The cadmium-based binder resin may include a functional group represented by the following formula (8) in at least one of both terminals.

[Chemical Formula 8]

In Formula 8,

Z ³ can be represented by the following formulas (8-1) to (8-7).

[Formula 8-1]

(Wherein 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 8-2]

[Formula 8-3]

[Formula 8-4]

[Formula 8-5]

(Wherein 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 8-6]

[Formula 8-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic 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; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

When the binder resin is a cadmium-based binder resin, the photosensitive resin composition containing the binder resin is excellent in developability, is excellent in sensitivity upon photo-curing, and is excellent in fine pattern formation.

The binder resin may be contained in an amount of 5% by weight to 30% by weight, for example, 7% by weight to 20% by weight based on the total amount of the photosensitive resin composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(C) Photopolymerization Monomer

The photopolymerizable monomer according to the present invention contains at least two functional groups represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

For example, the photopolymerizable monomer may contain 2 to 6 functional groups represented by the formula (1).

The photopolymerizable monomer contained in the photosensitive resin composition according to one embodiment contains at least two functional groups represented by the above formula (1), so that the curing reaction can proceed even at a low temperature of 150 ° C or lower. That is, the photosensitive resin composition according to one embodiment can form an organic film through a curing process even at a low temperature of 150 ° C or lower.

Further, the functional group represented by the above formula (1) in the photopolymerizable monomer has an ethylenically unsaturated double bond, so that sufficient polymerization can be performed during exposure in the pattern formation step, and a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

The photopolymerizable monomer may further include a linking group represented by the following general formulas (2) and (3).

(2)

(3)

In Formula 3,

L ² is a substituted or unsubstituted C1 to C10 alkylene group.

For example, the photopolymerizable monomer may include substituted or unsubstituted C1 to C10 polyoxyalkylene. The polyoxyalkylene may be connected to the functional group represented by the formula (1).

For example, the linking groups represented by formulas (2) and (3) may be concretely represented by the following formula (4).

[Chemical Formula 4]

In Formula 4,

m and n are each independently an integer of 1 to 10; For example, m and n may each independently be an integer of 1 to 5.

For example, each of L ³ to L ⁶ may independently be a substituted or unsubstituted C1 to C6 alkylene group. For example, each of L ³ to L ⁶ independently represents a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentyl Or a substituted or unsubstituted hexylene group, but is not limited thereto.

The photopolymerizable monomer may include a compound represented by the following formula (5), a compound represented by the following formula (6), or a combination thereof, but is not limited thereto.

[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)

p, q, r and s are each independently an integer of 1 to 10; For example, p, q, r and s may each independently be an integer of 1 to 5.

For example, when the photosensitive resin composition according to one embodiment contains both the compound represented by Chemical Formula 5 and the compound represented by Chemical Formula 6 as the photopolymerizable monomer, the compound represented by Chemical Formula 5 and the chemical compound represented by Chemical Formula 6 The compound may be included in a weight ratio of 3: 7 to 7: 3. When the two photopolymerizable monomers are used in the above ratio range, a film having a high curing rate and a high crosslinking density can be formed, which is advantageous in terms of heat resistance and chemical resistance.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 1 wt% to 20 wt%, for example, 5 wt% to 15 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the pattern is formed with sufficient curing during exposure in the step of pattern formation, so that the reliability is excellent, and the heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern are also excellent.

(D) Light curing Initiator

The photopolymerization initiator according to the present invention is an initiator generally used in a photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine- Can be used.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

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

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

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

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

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

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.5 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator sufficiently undergoes curing during exposure in the pattern formation step, thereby obtaining excellent reliability, and is excellent in heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern, .

(E) Solvent

The solvent according to the present invention may be a material which has compatibility with the photoconversion material, the binder resin, the photopolymerizable monomer and the photopolymerization initiator but does not react with the photopolymerization initiator.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl 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 methylethylcarbitol, diethylcarbitol, 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 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- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of 30% by weight to 80% by weight, for example, 40% by weight to 80% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the photosensitive organic film is excellent.

(F) Diffuser

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

For example, the diffusing material may include barium sulfate (BaSO _4), calcium carbonate (CaCO _3), titanium dioxide (TiO _2), zirconia (ZrO _2), or a combination thereof.

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

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

The diffusing agent may be included in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition. When the amount of the dispersing agent is less than 0.1% by weight based on the total amount of the photosensitive resin composition, it is difficult to expect the effect of improving the light conversion efficiency by using the dispersing agent. When the dispersing agent is contained in an amount exceeding 5% by weight, May be deteriorated.

(G) Other additives

The photosensitive resin composition according to one embodiment includes malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; 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 with a substrate or the like.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used singly or in combination of two or more.

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

The above-mentioned photosensitive resin composition may further contain a surfactant such as a fluorine-based surfactant for the purpose of improving coatability and preventing defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; 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; Fluorinated surfactants commercially available under the names F-482, F-484, F-478 and F-554 of DIC Co., Ltd. can be used.

The fluorine-based 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 fluorosurfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wettability to the glass substrate is excellent.

The photosensitive resin composition may contain a certain amount of other additives such as an antioxidant and a stabilizer within a range that does not impair the physical properties.

Another embodiment provides a photosensitive organic film prepared using the above-described photosensitive resin composition. The method for producing the photosensitive organic film is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is applied onto a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method, applicator method or the like to a desired thickness, for example, 1.2 탆 to 3.5 탆 After coating, the coating is formed by removing the solvent by heating at a temperature of 70 ° C to 90 ° C for 1 minute to 10 minutes.

(2) Exposure step

After forming a mask of a predetermined type in order to form a pattern necessary for the obtained coating film, an active line of 200 nm to 500 nm is irradiated. As the light source used for the 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, and the like can be used.

The exposure dose varies depending on the kind of each component of the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high pressure mercury lamp is used, the exposure dose is 500 mJ / cm ² (By a 365 nm sensor).

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

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

By using the above-described photosensitive resin composition, excellent heat resistance and chemical resistance can be obtained even in a low temperature process.

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

(Preparation of photosensitive resin composition)

Example One Embodiment 5 and Comparative Example 1 to Comparative Example 4

Using the following components, photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 to 4 were prepared with the compositions shown in Table 1 below.

Specifically, a photopolymerization initiator was dissolved in a solvent, followed by sufficient stirring at room temperature for 2 hours. Then, the photopolymerizable monomer and the acrylic binder resin were added together with the photo-conversion material (quantum dot) and stirred at room temperature for another 2 hours. After adding a dispersant and a fluorine surfactant 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) Photoconversion matter

InP / ZnS quantum dots (fluorescence lambda _em = 630 nm, FWHM = 45 nm, Red QD, Hansol Chemical Co.)

(B) Binder resin

Acrylic binder resin (SP-RY16, Showa denko)

(C) Photopolymerization Monomer

(C-1) A compound represented by the following formula (5-1) (LTM 1, manufactured by BASF)

[Formula 5-1]

(In the formula 5-1, p and q are each independently an integer of 2)

(C-2) A compound represented by the following formula (6-1) (LTM 2, manufactured by BASF)

[Formula 6-1]

(In the above formula (6-1), r and s are each independently an integer of 2)

(C-3) dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C-4) Polyethylene glycol 200 diacrylate (MIIS Corporation, M282)

(C-5) Bisphenol A (EO) 10 diacrylate (MWCM, M2100)

(D) Light curing Initiator

Oxime photopolymerization initiator (OXE02, BASF)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) Diffuser

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

(G) Other additives

Fluorine-based surfactant (DIC, F-554)

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Photoconductive material 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 (B) binder resin 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 (C)
Photopolymerizable monomer (C-1) 10.0 - 7.0 5.0 3.0 - - - - (C-2) - 10.0 3.0 5.0 7.0 - - - - (C-3) - - - - - 10.0 - - 10.0 (C-4) - - - - - - 10.0 - - (C-5) - - - - - - - 10.0 - (D) a photopolymerization initiator 0.998 0.998 0.998 0.998 0.998 0.998 0.998 0.998 0.998 (E) Solvent 70.0 70.0 70.0 70.0 70.0 70.0 70.0 70.0 71.0 (F) Diffusing agent 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - (G) Other additives 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 Sum 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0

Rating 1: PLQY (Photoluminescence Quantum yield) evaluation

15 ml of each of the photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were taken and coated on a glass substrate to a thickness of 3.5 탆 using a spin coater (Mikasa, Opticoat MS-A150) After soft-baking at 90 ° C for 3 minutes using a hot-plate, the substrate was irradiated with UV light at an output power of 50 mJ / cm ² using an exposure device (Ushio, ghi broadband) To form a primary coating film. Subsequently, development was carried out with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) using a developing machine (SVS, SSP-200). Thereafter, hard-baking was performed in a convection oven at 150 ° C or 230 ° C for 30 minutes to obtain a patterned photosensitive organic film.

The PLQY of the photosensitive resin composition (QDPR) prepared in Examples 1 to 5 and Comparative Examples 1 to 4 and the photosensitive organic film (QD film) prepared using the photosensitive resin composition was quantaurus-QY quantum yield spectrometer C11347-11 (Hamamatsu corporation, Japan). In general, PLQY can be obtained by using the following equation (1). The measured PLQY is shown in Table 2 below.

[Equation 1]

PLQY = Nmuber of photons as photoluminescence from sample / Number of photons absorbed by sample

Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Example 5 Hard-Baking Temperature (℃) 230 150 150 150 150 150 150 150 150 150 PLQY (%) QD PR 70-80 70-80 70-80 60-70 35-45 70-80 60-70 70-80 70-80 65-70 QD film 30 60 61 52 40 69 60 65 65 60

As shown in Table 2 above, the PLQY of QDPR was similar to that of Example 2, Example 5, and Comparative Example 3, and the PLQY on the QD PR solution was 70% to 80%. QD's QY is closely related to compatibility with solvents, photopolymerizable monomers and binder resins. In Comparative Example 3 using M2100 (C-5 in Table 1) having an aromatic structure as a photopolymerizable monomer, the dispersibility of QD is good It is believed that the lower QY was caused by the lower compatibility. On the other hand, in Examples 2 and 5 using a large number of hydroxy group-containing photopolymerizable monomers (C-2 in Table 1) alone or in excess, dispersibility of QD was good, but secondary aggregation and reabsorption occurred between QDs, QY, which is caused by a decrease in the amount of the drug.

In comparison with Comparative Example 1, PLQY of the QD film relative to the PLQY of the QDPR was remarkably reduced when the QDPR was treated with the hard-baking (230 ° C / 30min) of the conventional LCD color filter, In contrast, when the process conditions were applied at a low temperature (hard-baking: 150 ° C / 30min), the PLQY of the PD film versus the PLQY of the QDPR was not significantly decreased. As a result, a photosensitive organic film prepared using a photosensitive resin composition containing a photo-conversion material such as a quantum dot or the like is more suitable for a low-temperature process than a photosensitive organic film prepared using a photosensitive resin composition containing a color material such as a pigment or a dye .

Evaluation 2: Chemical resistance evaluation

The photosensitive organic film (QD film) of Evaluation 1 was immersed in a PI solvent for 5 minutes to measure changes in thickness and PLQY before and after immersion, and the results are shown in Table 3 below.

The thickness variation was analyzed by Alpha step (KLA Tencor), and the PLQY change was measured in the same manner as in Evaluation 1.

Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Example 5 Hard-Baking Temperature (℃) 230 150 150 150 150 150 150 150 150 150 Thickness Change (㎛) &Lt; 0.1 <2 peel-off peel-off <5 <0.2 &Lt; 0.1 &Lt; 0.1 &Lt; 0.1 &Lt; 0.1 PLQY Change (%) 5 50 NG NG NG 10 3 6 5 3

As shown in Table 3, since the chemical resistance is a value depending on the curing rate and the curing density, the chemical resistance was excellent when the curing was sufficiently performed as in Comparative Example 1 treated by the high temperature process. On the other hand, Comparative Example 1 treated with a low-temperature process had insufficient curing and a low hardness and a low density of the film, so that the chemical resistance was lower than that of the high-temperature process.

In the case of Comparative Example 2 and Comparative Example 3, it was treated in a low-temperature process and had a low curing density, so that it did not have resistance to the PI solvent and was peel-off. On the other hand, in Examples 1 to 5, in which the photopolymerizable monomer (C-1 and C-2 in Table 1) having a high curing rate due to a rapid curing reaction in the low temperature process was applied, the curing rate of Comparative Examples 2 and 3 And the chemical resistance of the examples in which the bifunctional photopolymerizable monomer having a large number of functional groups were used singly or in excess was slightly superior to the examples in which the bifunctional photopolymerizable monomer was used alone or in excess.

Evaluation 3: Fairness evaluation

15 ml of each of the photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were taken and coated on a glass substrate to a thickness of 3.5 탆 using a spin coater (Mikasa, Opticoat MS-A150) After soft-baking at 90 ° C for 3 minutes using a hot-plate, the substrate was irradiated with UV light at an output power of 50 mJ / cm ² using an exposure device (Ushio, ghi broadband) To form a primary coating film. Subsequently, the resultant was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) using a developing machine (SVS, SSP-200) and patterned. The resultant was dried for 1 minute by an air conditioner, And the pattern characteristics were visually observed and judged (excellent / poor). The adhesion was judged to be 10 μm pattern implementation (○ / Ⅹ). The results of the fairness evaluation are shown in Table 4 and Figs. 4 to 6 below. (FIG. 4 is a photograph of Comparative Example 1 in a high temperature process, FIG. 5 is a photograph of Example 2, and FIG. 6 is a photograph of Example 3).

Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Example 5 Hard-Baking Temperature (℃) 230 150 150 150 150 150 150 150 150 150 Pattern characteristics Great Great lack lack lack Great Great Great Great Great Adhesion ○ X X X X ○ ○ ○ ○ ○

As shown in Table 4 and FIG. 4 to FIG. 6, in the case of Examples 1 to 5, the pattern characteristics which are equivalent to those of Comparative Example 1 in the high temperature process and which are higher than those of Comparative Examples 1 to 4 in the low temperature process Adhesive strength.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims

(A) a photo-conversion material;
(B) a binder resin;
(C) a photopolymerizable monomer comprising a compound represented by the following formula (5) and a compound represented by the following formula (6) in a weight ratio of 3: 7 to 7: 3;
(D) a photopolymerization initiator; And
(E) Solvent
: &Lt; EMI ID =
[Chemical Formula 5]

[Chemical Formula 6]

In the above formulas (5) and (6)
p, q, r and s are each independently an integer of 1 to 10;

delete

The method according to claim 1,
The photosensitive resin composition further comprises (F) a diffusing agent.

8. The method of claim 7,
Wherein the diffusing agent comprises barium sulfate, calcium carbonate, titanium dioxide or a combination thereof.

8. The method of claim 7,
Wherein the diffusing agent is contained in an amount of 0.1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition.

8. The method of claim 7,
Wherein the diffusing agent has an average particle diameter (D ₅₀ ) of 150 nm to 250 nm.

The method according to claim 1,
Wherein the photoconversion material absorbs light in a wavelength range of 360 nm to 780 nm and emits fluorescence in a wavelength range of 580 nm to 700 nm.

12. The method of claim 11,
Wherein the photo-conversion material is a quantum dot.

The method according to claim 1,
The photosensitive resin composition preferably contains, relative to the total amount of the photosensitive resin composition,
1% to 30% by weight of the photo-conversion material (A);
5 to 30% by weight of the binder resin (B);
1 to 20% by weight of the (C) photopolymerizable monomer;
0.1 to 5% by weight of the photopolymerization initiator (D); And
The amount of the solvent (E)
.

The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; Or a combination thereof.

A photosensitive organic film produced by using the photosensitive resin composition of any one of claims 1 to 14.

A color filter comprising the photosensitive organic film of claim 15.