KR102244467B1 - Photosensitive resin composition, black pixel defining layer using the same and display device - Google Patents

Abstract

[화학식 2]

(상기 화학식 1 및 화학식 2에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) alkali-soluble resin; (B) a black colorant; (C) photopolymerizable monomer; (D) photoinitiator; (E) an antioxidant containing a functional group represented by the following formula (1) or (2); And (F) a photosensitive resin composition including a solvent, a photosensitive resin film prepared using the same, and a display device including the photosensitive resin film.
[Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2, each substituent is as defined in the specification.)

Description

Photosensitive resin composition, photosensitive resin film and display device using the same {PHOTOSENSITIVE RESIN COMPOSITION, BLACK PIXEL DEFINING LAYER USING THE SAME AND DISPLAY DEVICE}

The present description relates to a photosensitive resin composition, a photosensitive resin film and a display device using the same.

The photosensitive resin composition is an essential material for manufacturing display devices such as color filters, liquid crystal display materials, display devices such as organic light emitting devices, and display device panel materials. For example, in a color filter such as a color liquid crystal display, in order to increase the display contrast or color development effect, a photosensitive layer such as a black pixel partition layer is placed at the boundary between colored layers such as red, green, and blue. A resin film is required, and this photosensitive resin film is formed mainly from a photosensitive resin composition.

In particular, a photosensitive resin film such as a pixel partition layer used as a material for a display device panel must have a low taper angle in order to have processability and device reliability. In addition, a colorant such as a pigment or dye that absorbs light in the visible region should be used for shading.

However, the conventional photosensitive resin composition has a problem of deteriorating the life characteristics of a device adjacent to the resin film made of the composition due to outgassing.

Therefore, research to develop a photosensitive resin composition capable of solving the above problem is ongoing.

One embodiment is to provide a photosensitive resin composition capable of improving the room temperature driving life of a device while preventing a decrease in sensitivity.

Another embodiment is to provide a photosensitive resin film prepared by using the photosensitive resin composition.

Another embodiment is to provide a display device including the photosensitive resin film.

One embodiment is (A) an alkali-soluble resin; (B) a black colorant; (C) photopolymerizable monomer; (D) photoinitiator; (E) an antioxidant containing a functional group represented by the following formula (1) or (2); And (F) It provides a photosensitive resin composition containing a solvent.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ is represented by any one of the following formulas P-1 to P-4,

R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

[Formula P-1]

[Formula P-2]

[Formula P-3]

[Formula P-4]

In Formulas P-1 to P-4,

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

R ⁶ and R ⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ⁸ to R ¹⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The antioxidant may further include a functional group represented by any one of the following Chemical Formulas 3-1 to 3-3.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

In Formula 3-1 to Formula 3-3,

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

R ¹² to R ¹⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

** is a moiety connected to * in Chemical Formulas 1 and 2.

The antioxidant may further include a linking group represented by Formula 4-1 or Formula 4-2 below.

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ⁵ to L ⁷ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

L ⁸ is a substituted or unsubstituted C1 to C20 alkylene group, an oxygen atom or a sulfur atom,

n is an integer from 1 to 10,

** is a moiety connected to * in Chemical Formulas 1 and 2.

The antioxidant may be represented by the following Formula 5-1 or Formula 5-2.

[Chemical Formula 5-1]

[Chemical Formula 5-2]

In Formula 5-1 and Formula 5-2,

R ¹ is represented by any one of Formulas P-1 to P-4,

R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

L ⁹ and L ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The antioxidant may be represented by any one of the following Chemical Formulas 6-1 to 6-14.

[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

[Formula 6-5]

[Formula 6-6]

[Formula 6-7]

[Formula 6-8]

[Chemical Formula 6-9]

[Chemical Formula 6-10]

[Chemical Formula 6-11]

[Chemical Formula 6-12]

[Chemical Formula 6-13]

[Formula 6-14]

The antioxidant may be included in an amount of 0.1% to 5.0% by weight based on the total amount of solids constituting the photosensitive resin composition.

The alkali-soluble resin may include a polymer having a glass transition temperature of 150°C or less.

The polymer having a glass transition temperature of 150° C. or less may include a structural unit represented by Formula 7 below, a structural unit represented by Formula 8 below, or a combination thereof.

[Formula 7]

[Formula 8]

In Formula 7 and Formula 8,

X ¹ to X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,

Y ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

L ¹¹ and L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹⁶ to R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

The alkali-soluble resin may further include a cardo-based binder resin.

The black colorant may include an inorganic black pigment, an organic black pigment, or a combination thereof.

The black colorant may be a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a violet pigment.

The photosensitive resin composition, based on the total amount of solids constituting the photosensitive resin composition, the (A) alkali-soluble resin 30% by weight to 50% by weight; 30 to 65% by weight of the (B) black colorant; 1% to 10% by weight of the (C) photopolymerizable monomer; (D) 0.01% to 5% by weight of the photopolymerization initiator; And 0.1% to 5.0% by weight of the (E) antioxidant.

The photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

The photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

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

Another embodiment provides a display device including the photosensitive resin film.

The display device may be an organic light emitting device (OLED).

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

The photosensitive resin composition according to an embodiment may improve the room temperature life characteristics of an organic light emitting device while minimizing a decrease in sensitivity.

1 is a light emission photograph of a device including a photosensitive resin film prepared using the photosensitive resin composition according to Example 4.
FIG. 2 is a further enlarged photograph of a light emission photograph of a device including a photosensitive resin film prepared using the photosensitive resin composition according to Example 4. FIG.

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

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

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

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

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

In the present specification, unless otherwise defined, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

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

In the present specification, the cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 9-1 to 9-11 are included in the backbone of the resin.

In the present specification, unless otherwise defined, "*" and "**" mean the same or different atoms (including hydrogen atoms) or a moiety connected with a chemical formula.

The photosensitive resin composition according to an embodiment includes (A) an alkali-soluble resin; (B) a black colorant; (C) photopolymerizable monomer; (D) photoinitiator; (E) an antioxidant containing a functional group represented by the following formula (1) or (2); And (F) a solvent.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ is represented by any one of the following formulas P-1 to P-4,

R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

[Formula P-1]

[Formula P-2]

[Formula P-3]

[Formula P-4]

In Formulas P-1 to P-4,

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

R ⁶ and R ⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ⁸ to R ¹⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

Current planarization materials or barrier materials have a transparent, yellowish or redish brown color. As a result, light entering the device from the outside is reflected by the metal layer, so that the black color of the device is deteriorated when the device is powered off, and there are problems such as low external visibility, and a decrease in luminance at a low angle. In addition, as OLED devices are becoming more transparent and flexible, there is an increasing need to blacken the planarization film and barrier material. In order to perform patterning without residues underneath while blackening the resist, it is advantageous to develop in a negative type. Resist for use can affect the lifetime of OLED devices due to outgassing, oxygen, and water vapor.

Accordingly, the inventors of the present invention used an antioxidant having a specific structure in a negative resist in order to improve the normal temperature driving life of an OLED device after a long study, and acrylate radicals generated during OLED driving affect the life of the device. Could be prevented.

Hereinafter, each component will be described in detail.

(E) antioxidant

The photosensitive resin composition according to an embodiment includes an antioxidant, and the antioxidant can remove acrylate radicals generated when driving a display device such as an OLED including a functional group represented by Formula 1 or Formula 2 , It is possible to prevent the deterioration of the normal temperature driving life of the display device. In particular, the acrylate radical is generated by heat, and the antioxidant has a structure including a functional group represented by Formula 1 or Formula 2, and thus does not play a role as an antioxidant before thermal curing, and is oxidized only after thermal curing. Since it serves as an inhibitor, it is possible to prevent deterioration in life characteristics of the device without significantly affecting other characteristics of the device.

For example, the antioxidant may further include a functional group represented by any one of the following Formulas 3-1 to 3-3.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

In Formula 3-1 to Formula 3-3,

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

R ¹² to R ¹⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

** is a moiety connected to * in Chemical Formulas 1 and 2.

For example, the antioxidant may further include a linking group represented by Formula 4-1 or Formula 4-2 below.

[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,

L ⁵ to L ⁷ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

L ⁸ is a substituted or unsubstituted C1 to C20 alkylene group, an oxygen atom or a sulfur atom,

n is an integer from 1 to 10,

** is a moiety connected to * in Chemical Formulas 1 and 2.

For example, the antioxidant may be represented by the following Formula 5-1 or Formula 5-2.

[Chemical Formula 5-1]

[Chemical Formula 5-2]

In Formula 5-1 and Formula 5-2,

R ¹ is represented by any one of the following formulas P-1 to P-4,

R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,

L ⁹ and L ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

[Formula P-1]

[Formula P-2]

[Formula P-3]

[Formula P-4]

In Formulas P-1 to P-4,

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

R ⁶ and R ⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

R ⁸ to R ¹⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the antioxidant may be represented by any one of Formulas 6-1 to 6-14, but is not limited thereto.

[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

[Formula 6-5]

[Formula 6-6]

[Formula 6-7]

[Formula 6-8]

[Chemical Formula 6-9]

[Chemical Formula 6-10]

[Chemical Formula 6-11]

[Chemical Formula 6-12]

[Chemical Formula 6-13]

[Formula 6-14]

The antioxidant may be included in an amount of 0.1% to 5.0% by weight, such as 0.1% to 3.0% by weight, based on the total amount of solids constituting the photosensitive resin composition. When the antioxidant is included in the above range, acrylate radicals generated during driving of the device can be more easily removed, thereby more effectively preventing deterioration in device lifetime characteristics.

(A) alkali-soluble resin

The alkali-soluble resin in the photosensitive resin composition according to an embodiment may include a polymer having a glass transition temperature of 150°C or less.

The photosensitive resin composition can be used as a light-shielding material including a black colorant, and having a taper angle of 45° or less is advantageous for EL deposition, and the alkali-soluble resin is a polymer having a glass transition temperature of 150°C or less. If included, the taper angle can be maintained below 45˚.

The polymer having a glass transition temperature of 150° C. or less may include a polymer having a structural unit represented by Formula 7 below, a structural unit represented by Formula 8 below, or a combination thereof.

[Formula 7]

[Formula 8]

In Formula 7 and Formula 8,

X ¹ to X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,

Y ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

L ¹¹ and L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹⁶ to R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

The polymer represented by Chemical Formula 7 has excellent heat resistance, and thus can be applied as a dispersion binder in a dispersion, has a great effect on reducing outgassing, and can prevent deterioration in life characteristics of the device together with the antioxidant. That is, the antioxidant may prevent deterioration of lifespan characteristics of the device by removing acrylate radicals generated during driving of the device, and the polymer represented by Chemical Formula 7 may prevent deterioration of lifespan characteristics of the device by reducing outgassing.

For example, Formula 7 may be represented by the following Formula 7-1, and Formula 8 may be represented by the following Formula 8-1.

[Chemical Formula 7-1]

[Chemical Formula 8-1]

In Formula 7-1 and Formula 8-1,

R ^x , R ^y and R ¹⁶ to R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group,

p1 and p2 are each independently an integer of 1 to 10.

For example, R ^x and R ^y may each independently be a C1 to C20 alkyl group substituted with a fluoro group, such as a trifluoromethyl group.

The alkali-soluble resin may further include a cardo-based binder resin.

The cardo-based binder resin may be represented by Formula 9 below.

[Formula 9]

In Chemical Formula 9,

R ⁵¹ and R ⁵² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ⁵³ and R ⁵⁴ 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 ⁵⁵ R ⁵⁶ , SiR ⁵⁷ R ⁵⁸ (wherein R ⁵⁵ to R ⁵⁸ are each independently a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group) or It is any one of the linking groups represented by the following formulas 9-1 to 9-11,

[Chemical Formula 9-1]

[Chemical Formula 9-2]

[Chemical Formula 9-3]

[Chemical Formula 9-4]

[Chemical Formula 9-5]

(In Formula 9-5,

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.)

[Chemical Formula 9-6]

[Chemical Formula 9-7]

[Chemical Formula 9-8]

[Chemical Formula 9-9]

[Chemical Formula 9-10]

[Chemical Formula 9-11]

Z ² is an acid dianhydride residue,

n1 and n2 are each independently an integer of 0 to 4.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, 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, a pattern can be formed well without residues when the light shielding layer is manufactured, there is no loss of film thickness during development, and a good pattern can be obtained.

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

[Formula 10]

In Chemical Formula 10,

Z ³ may be represented by the following Chemical Formulas 10-1 to 10-7.

[Formula 10-1]

(In Formula 10-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

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

[Formula 10-6]

[Formula 10-7]

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

As described above, when the binder resin according to an embodiment contains only the cardo-based binder resin alone, the phenomenon may be too fast, and the taper characteristics may be greatly deteriorated (T-top profile observed). For the alkali-soluble resin, it is preferable to use the polymer having a glass transition temperature of 150°C or less and the cardo-based binder resin together, and more preferably, the polymer having a glass transition temperature of 150°C or less is the cardo-based resin. It may be included in a larger amount than the binder resin.

The alkali-soluble resin may have a weight average molecular weight of 3,000 g/mol to 20,000 g/mol. When the weight average molecular weight of the alkali-soluble resin is within the above range, it has excellent pattern formation, and the prepared thin film may have excellent mechanical and thermal properties.

The alkali-soluble resin may be included in an amount of 30% to 50% by weight, such as 35% to 45% by weight, based on the total amount of solids constituting the photosensitive resin composition. When the alkali-soluble resin is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(B) black colorant

The black colorant may include a pigment, dye, or a combination thereof having high transmittance in the ultraviolet region (300 nm to 400 nm wavelength region) and high light-shielding property in the visible region in order to increase photocuring efficiency.

Specifically, the black colorant has a value of "maximum transmittance in a wavelength range of 350nm to 400nm / transmittance in a wavelength of 550nm" of 1.5 or more.

The inventors of the present invention, after repeated research, when using a black colorant having a value of 1.5 or more of "maximum transmittance in the 350nm to 400nm wavelength range / transmittance in the 550nm wavelength" when preparing a photosensitive resin composition, In addition, through a light source in the UV range, it has excellent heat resistance by increasing photocurability. Also, the high transmittance of the UV range makes it possible to easily align, so that the exposure process can be easily performed. It was confirmed that it can be implemented. The 550nm wavelength is the wavelength at the time of measuring the optical density, and 350nm to 400nm is the wavelength range where the photopolymerization initiator most efficiently initiates the photoinitiation reaction.The photopolymerization initiator is the most efficient photoinitiation reaction compared to the transmittance at the wavelength at the time of measuring the optical density. The higher the maximum transmittance in the wavelength region causing the light, the better the light blocking of visible light and the heat resistance through the light source in the UV region can be obtained.In particular, the photopolymerization initiator is the most efficient initiating light compared to the transmittance at the wavelength when measuring the optical density. When the maximum transmittance in the wavelength region causing the reaction has a value of 1.5 times or more, the photocombination efficiency and heat resistance can be greatly increased, and at the same time, the transmittance in the infrared wavelength region is also high, making the exposure process easier and 1㎛ It is also possible to implement a level of step difference.

For example, the black colorant may include an inorganic black pigment, an organic black pigment, or a combination thereof.

For example, the black colorant may be an organic black pigment.

When inorganic black pigments such as aniline black, perylene black, titanium black, and carbon black are used alone as a black colorant, excellent light-shielding properties can be achieved, but the development process is performed in a state where only surface curing is performed without internal curing. It can be difficult to maximize the process margin.

For example, the organic black pigment may include a red pigment, a green pigment, a blue pigment, a violet pigment, or a combination thereof. For example, the organic black pigment may be a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a violet pigment.

The red pigment is CI red pigment 179, CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red pigment within the Color Index. 89 and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

The green pigment is C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment green 62 and the like may be mentioned, and these may be used alone or in combination of two or more, but are not limited thereto.

The blue pigment is C.I. Blue pigment 15:6, C.I. Blue pigment 15:0, C.I. Blue pigment 15:1, C.I. Blue pigment 15:2, C.I. Blue pigment 15:3, C.I. Blue pigment 15:4, C.I. Blue pigment 15:5, C.I blue pigment 15:6, C.I. Blue pigment 16 and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

The violet pigment is C.I. Violet pigment 29, dioxazine violet, first violet B, methyl violet lake, indanthrene brilliant violet, and the like may be used, and these may be used alone or in combination of two or more, but are not limited thereto.

For example, the black colorant according to an embodiment may be used in the form of a dispersion, and the dispersion may include a solid pigment, a dispersant, a solvent, and the like. In this case, the solid pigment may be included in an amount of 5% to 30% by weight, for example, 8% to 15% by weight, based on the total amount of the pigment dispersion. In this case, effective dispersion of the pigment can be achieved, and dispersion stability can be ensured.

The black colorant may have a maximum transmittance value in a wavelength region of 800 nm or more than a maximum transmittance value in a wavelength region of 450 nm to 700 nm. That is, the black colorant also has a high transmittance to light in the infrared region, so that the patterning process is efficiently performed.

The black colorant may be included in an amount of 30% to 65% by weight, such as 40% to 60% by weight, based on the total amount of solids constituting the photosensitive resin composition. When the black colorant is included within the above range, the coloring effect and development performance are excellent.

(C) photopolymerizable monomer

The photopolymerizable monomer in the photosensitive resin composition according to an embodiment may be a single compound or a mixture of two different compounds.

When the photopolymerizable monomer is a mixture of two different compounds, any one of the two compounds may be a compound containing at least two or more functional groups represented by the following formula (11).

[Formula 11]

In Formula 11,

R ¹⁰⁰ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹⁰⁰ is a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

For example, a compound including at least two or more functional groups represented by Formula 11 may include 2 to 6 functional groups represented by Formula 11. In this case, sufficient polymerization may occur during exposure in the pattern formation process to form a pattern having excellent heat resistance, light resistance, and chemical resistance.

For example, the compound including at least two or more functional groups represented by Formula 11 may be a compound represented by Formula 12 or Formula 13.

[Formula 12]

[Formula 13]

In Formula 12 and Formula 13,

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

When the photopolymerizable monomer is a mixture of two different compounds, the other of the two compounds may be a monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond. have.

The monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond is, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di ( Meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipenta Erythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 　bisphenol A epoxy(meth)acrylate , Ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate 　 or a combination thereof.

For example, a commercially available product of the monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond is as follows. The (meth) acrylic acid is one example of a polyfunctional ester, doah Gosei cultivating the T (weeks)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®, and the like; ^{KAYARAD TC-110S ®} of Nihon Kayaku Co., Ltd., TC-120S ^®, etc.; Osaka yukki cultivate may be a T (weeks)社of ^{V-158 ®, V-2311} ® and the like. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei cultivating the T (weeks)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^{®; KAYARAD HDDA ®} , HX-220 ^® , R-604 ^{® of} Nihon Kayaku Co., Ltd.; ^{Examples include V-260 ®} , V-312 ^® , and V-335 HP ^{® from} Osaka Yuki Chemical High School Co., Ltd. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei the cultivating T (weeks)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M ^® -7100, Dong M-8030 ^®, same M-8060 ^®, and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; ^{V-295 ®} , East-300 ^® , East-360 ^® , East-GPT ^® , East-3PA ^® , and East-400 ^{® from} Osaka Yukigayaku High School Co., Ltd. are listed. The above products can be used alone or in combination of two or more.

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

The photopolymerizable monomer may be included in an amount of 1% to 10% by weight, such as 1% to 5% by weight, based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, 　 curing occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, heat resistance, light resistance and chemical resistance of the pattern, and resolution and adhesion are also excellent.

(D) photopolymerization initiator

The photosensitive resin composition according to an embodiment includes a photopolymerization initiator. The photoinitiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

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

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 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-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diiso And propyl thioxanthone.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho1-yl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(triclo Romethyl)-6-piperonyl-s-triazine, 2-4-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-(O-acetyloxime) -1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane 1-one, 1-(4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2- Dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octan-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime -O-acetate can be used.

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

The photopolymerization initiator may be included in an amount of 0.01% to 5% by weight, such as 0.1% to 3% by weight, based on the total amount of solids constituting the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently during exposure in a pattern formation process for manufacturing a color filter, so that sensitivity is excellent and transmittance is improved.

(F) solvent

The solvent may be materials that have compatibility with the antioxidant, the black colorant, the alkali-soluble resin, the photopolymerizable monomer, and the photopolymerization initiator, 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, ethylene glycol monoethyl ether, and ethylene glycol dimethyl 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 ethyl methyl 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; Lactate esters such as methyl lactate and ethyl lactate; Oxyacetate alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxypropionate alkyl esters such as 3-oxypropionate methyl and 3-oxypropionate ethyl; 3-alkoxypropionate alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionate alkyl esters such as 2-oxypropionate methyl, 2-oxypropionate ethyl, and 2-oxypropionate propyl; 2-alkoxy propionate alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-methylpropionic acid esters such as 2-oxy-2-methylpropionate methyl and 2-oxy-2-methylethylpropionate, 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2- Monooxymonocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate; 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, etc., and also N-methylformamide, N,N-dimethylformamide, N-methylformanilad, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, 3-methylbenzoic acid, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; 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, propylene glycol propyl ether acetate, 3-methylbenzoic acid, and the like can be used.

The solvent may be included in a residual amount, such as 35% to 80% by weight, such as 40% to 70% by weight, based on the total amount (solid content and solvent) of the photosensitive resin composition. When the solvent is included within the above range, since the photosensitive resin composition has an appropriate viscosity, fairness is excellent in manufacturing a photosensitive resin film such as a black pixel partition layer.

(G) other additives

Meanwhile, the photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, and γ-gly Cidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

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

In addition, the photosensitive resin composition may further include a surfactant, a surfactant, such as a fluorine-based surfactant, and/or a silicone-based surfactant, to improve coating properties and prevent defects from being generated, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; ^{Mechapack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® of} Dai Nippon Ink and Chemical High School Co., Ltd.; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; May be selected from commercially available under the name, such as Toray Silicone ^® (Note)社SH-28PA, the copper ^® -190, copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

As the silicone surfactant, BYK Chem's BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, A commercially available product such as BYK-325 can be used.

The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the above range, coating uniformity is ensured, stains do not occur, and wetting properties for IZO substrates or glass substrates are excellent.

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

The photosensitive resin composition according to an embodiment may be a positive type or a negative type, but in order to more completely remove the residue of the area where the pattern is exposed after exposure and development of the composition having a light-shielding property, it is more of a negative type. desirable.

Another embodiment provides a photosensitive resin film, such as a black pixel partition wall layer, prepared by exposing, developing, and curing the above-described photosensitive resin composition.

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

(1) Application and film formation step

After applying the photosensitive resin composition to a desired thickness on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment using a method such as spin or slit coating, roll coating, screen printing, and applicator method, The photosensitive resin film is formed by heating at °C to 110 °C for 1 to 10 minutes to remove the solvent.

(2) exposure step

After interposing a mask to form a necessary pattern on the obtained photosensitive resin film, active rays of 200 nm to 500 nm are irradiated. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, and the like may be used.

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

(3) development stage

As a developing method, after the exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, thereby forming a pattern by leaving only the exposed portions.

(4) Post-processing step

There is a post-heating process for obtaining an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability for the image pattern obtained by development in the above process. For example, after development, it may be heated in a convection oven at 250° C. for 1 hour.

Another embodiment provides a display device including the photosensitive resin film.

The display device may be an organic light emitting device (OLED).

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

(Synthesis of copolymer)

Synthesis Example 1

61.5 g of dimethylacetamide was added while passing nitrogen into a 4-neck flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, and 12.3 g of 6-FDA (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride) was dissolved. . When the solid was completely dissolved, 3.27 g of SiDA ([Bis(3-aminopropyl)]polydimethylsiloxane) [PAM-E, Shin-Etsu Chemical Co., Ltd.] was added and stirred at room temperature for 2 hours. After the temperature was raised to 90° C., 7.96 g of pyridine and 5.14 g of acetic anhydride (Ac ₂ O) were added, followed by stirring for 3 hours. The temperature in the reactor was cooled to room temperature, and 0.33 g of HEMA was added, followed by stirring for 6 hours. Thereafter, the reaction mixture was added to water to generate a precipitate, and the precipitate was filtered and sufficiently washed with water, and then reduced at a temperature of 50° C. and dried for 24 hours or more to prepare a copolymer represented by the following formula E-1. The polymer had a weight average molecular weight of 13,800 g/mol calculated by GPC method in terms of standard polystyrene, a dispersion degree of 1.86, and a glass transition temperature of 46°C.

[Formula E-1]

(Production of photosensitive resin composition)

Examples 1 to 14, Comparative Example 1 and Comparative Example 2

According to the composition shown in Table 1 below, a photopolymerization initiator (SPI-02, Samyang) was dissolved in a solvent (PGMEA and 3-MBA (3-methylbenzoic acid)), followed by stirring at room temperature for 2 hours. Here, as an alkali-soluble resin, the copolymer (A) represented by the above formula E-1, cardo resin (KBR-101, Kyungin Corporation, weight average molecular weight: 2,000 g/mol) (B), photopolymerizable monomer (DPHA , Japanese powder) and an antioxidant were added, followed by stirring at room temperature for 1 hour. Here, a mixture of a black colorant (RBV: CI red pigment 179, CI. blue pigment 15:6 and CI violet pigment 29 (mixing ratio (w/w/w) = 47/38/15)) was added, After stirring at room temperature for 1 hour, the entire solution was stirred for 2 hours. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

(Unit: g) Black colorant Alkali-soluble resin Photopolymerizable monomer Photopolymerization initiator menstruum Antioxidant (A) (B) PEGMEA 3-MBA Example 1 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23
(Chemical Formula 6-1, SMS company, AO-1) Example 2 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-2, SMS company, AO-2) Example 3 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-3, SMS company, AO-3) Example 4 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-4, SMS company, AO-4) Example 5 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-5, SMS company, AO-5) Example 6 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-6, SMS company, AO-6) Example 7 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-7, SMS company, AO-7) Example 8 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-8, SMS company, AO-8) Example 9 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-9, SMS company, AO-9) Example 10 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-10, SMS company, AO-10) Example 11 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-11, SMS company, AO-11) Example 12 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-12, SMS company, AO-12) Example 13 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-13, SMS company, AO-13) Example 14 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Chemical Formula 6-14, SMS company, AO-14) Comparative Example 1 22 11.32 4.83 1.44 0.46 50.91 8.64 - Comparative Example 2 22 10.9 4.65 1.39 0.44 50.91 9.07 0.23 (Songwon Industries, IRG1076)

(evaluation)

Evaluation 1: Sensitivity

The photosensitive resin compositions according to Examples 1 to 14, Comparative Example 1 and Comparative Example 2 were applied to 10cm*10cm ITO glass (resistance 30Ω), heated on a hot plate at 100°C for 1 minute in proxy type, and then again A 1 µm-thick photosensitive resist film was formed by heating in contact type for 1 minute. After exposing the substrate coated with the photosensitive resist film with a varying amount of exposure with Ushio's UX-1200SM-AKS02 using a mask with patterns of various sizes, developed at room temperature with 2.38% TMAH solution to dissolve the exposed part. After removing it, it was washed with pure water for 50 seconds to form a pattern. Sensitivity was measured by confirming the energy at which the 20 µm pattern was implemented based on the pattern size measured using the MX51T-N633MU of Olympus Co., Ltd. for the size of the 20 µm square pattern, and the results are shown in Table 2 below.

Evaluation 2: room temperature life

The photosensitive resin composition according to Examples 1 to 14, Comparative Example 1 and Comparative Example 2 was applied to 10cm*10cm ITO glass (for simple panel production, AMG), and in a hot plate at 100°C, in proxy type for 1 minute. After heating, the contact type was heated again for 1 minute to form a 1 µm-thick photosensitive resist film. After exposing the substrate coated with the photosensitive resist film with a varying amount of exposure with Ushio's UX-1200SM-AKS02 using a mask with patterns of various sizes, developed at room temperature with 2.38% TMAH solution to dissolve the exposed part. After removing it, it was washed with pure water for 50 seconds to form a pattern. Thereafter, it was cured for 1 hour under the condition of 250° C. N _2. Subsequently, the evaporation materials were sequentially deposited and sealed to prepare TEG for evaluation. After completion of production, IVL (Current-Voltage-Luminance) was checked and room temperature (25°C) was started to continuously monitor the decrease in luminance and time was measured, and the results are shown in Table 2 below.

Sensitivity
(mJ/cm ² ) Room temperature driving life
(Time until luminance decrease 97%) Example 1 30 260 hours Example 2 35 265 hours Example 3 30 260 hours Example 4 30 265 hours Example 5 40 265 hours Example 6 30 260 hours Example 7 30 255 hours Example 8 35 260 hours Example 9 35 260 hours Example 10 30 270 hours Example 11 30 265 hours Example 12 35 255 hours Example 13 30 265 hours Example 14 40 260 hours Comparative Example 1 30 150 hours Comparative Example 2 150 220 hours

As shown in Table 2, the photosensitive resin composition according to an embodiment uses an antioxidant having a specific structure, so that sensitivity reduction is not greater than that of the photosensitive resin composition not containing the antioxidant of the structure, and at the same time, the room temperature driving life of the device It can be seen that it can be greatly improved.

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

Claims (15)

(A) an alkali-soluble resin containing a polymer having a glass transition temperature of 150°C or less;
(B) a black colorant;
(C) photopolymerizable monomer;
(D) photoinitiator;
(E) an antioxidant containing a functional group represented by the following formula (1) or (2); And
(F) solvent
Photosensitive resin composition comprising:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ¹ is represented by any one of the following formulas P-1 to P-4,
R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,
However, when R ¹ is represented by the following formula P-1, ^{at least one of R 2} to R ⁵ is a substituted or unsubstituted C1 to C20 alkoxy group,
When R ¹ is represented by the following Formula P-4, the antioxidant further includes a linking group represented by the following Formula 4-1 or Formula 4-2,
[Formula P-1]

[Formula P-2]

[Formula P-3]

[Formula P-4]

In Formulas P-1 to P-4,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ⁶ and R ⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ⁸ to R ¹⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
[Formula 4-1]

[Formula 4-2]

In Formula 4-1 and Formula 4-2,
L ⁵ to L ⁷ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
L ⁸ is a substituted or unsubstituted C1 to C20 alkylene group, an oxygen atom or a sulfur atom,
n is an integer from 1 to 10,
** is a moiety connected to * in Chemical Formulas 1 and 2.
The method of claim 1,
The antioxidant is a photosensitive resin composition further comprising a functional group represented by any one of the following Formulas 3-1 to 3-3:
[Chemical Formula 3-1]

[Chemical Formula 3-2]

[Chemical Formula 3-3]

In Formula 3-1 to Formula 3-3,
L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹² to R ¹⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
** is a moiety connected to * in Chemical Formulas 1 and 2.
delete The method of claim 1,
The antioxidant is a photosensitive resin composition represented by the following formula 5-2.
[Chemical Formula 5-2]

In Formula 5-2,
R ¹ is represented by any one of the following formulas P-1 to P-4,
R ² to R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C1 to C20 alkoxy group,
However, when R ¹ is represented by the following formula P-1, ^{at least one of R 2} to R ⁵ is a substituted or unsubstituted C1 to C20 alkoxy group,
When R ¹ is represented by the following Formula P-4, the antioxidant further includes a linking group represented by Formula 4-1 or Formula 4-2,
L ⁹ and L ¹⁰ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
[Formula P-1]

[Formula P-2]

[Formula P-3]

[Formula P-4]

In Formulas P-1 to P-4,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ⁶ and R ⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ⁸ to R ¹⁰ are each independently a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
The method of claim 1,
The antioxidant is a photosensitive resin composition represented by any one of the following Chemical Formulas 6-1 to 6-4, Chemical Formula 6-6, Chemical Formula 6-7, and Chemical Formula 6-9 to Chemical Formula 6-13.
[Chemical Formula 6-1]

[Formula 6-2]

[Chemical Formula 6-3]

[Chemical Formula 6-4]

[Formula 6-6]

[Formula 6-7]

[Chemical Formula 6-9]

[Chemical Formula 6-10]

[Chemical Formula 6-11]

[Chemical Formula 6-12]

[Chemical Formula 6-13]

The method of claim 1,
The photosensitive resin composition, wherein the antioxidant is contained in an amount of 0.1% to 5.0% by weight based on the total amount of solids constituting the photosensitive resin composition.
delete The method of claim 1,
The polymer having a glass transition temperature of 150° C. or less is a photosensitive resin composition comprising a structural unit represented by the following formula (7), a structural unit represented by the following formula (8), or a combination thereof:
[Formula 7]

[Formula 8]

In Formula 7 and Formula 8,
X ¹ to X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,
Y ¹ is a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,
L ¹¹ and L ¹² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹⁶ to R ¹⁹ are each independently a substituted or unsubstituted C1 to C20 alkyl group.
The method of claim 1,
The alkali-soluble resin is a photosensitive resin composition further comprising a cardo-based binder resin.
The method of claim 1,
The black colorant is a photosensitive resin composition comprising an inorganic black pigment, an organic black pigment, or a combination thereof.
The method of claim 1,
The black colorant is a photosensitive resin composition that is a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a violet pigment.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of solids constituting the photosensitive resin composition,
(A) 30% to 50% by weight of the alkali-soluble resin;
30 to 65% by weight of the (B) black colorant;
1% to 10% by weight of the (C) photopolymerizable monomer;
(D) 0.01% to 5% by weight of the photopolymerization initiator; And
0.1% to 5.0% by weight of the (E) antioxidant
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film prepared using the photosensitive resin composition of any one of claims 1, 2, 4 to 6, and 8 to 13.
A display element comprising the photosensitive resin film of claim 14.

Images