KR102244472B1 - Photosensitive resin composition, black pixel defining layer using the same and display device - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) alkali-soluble resin; (B) a black colorant; (C) photopolymerizable monomer; (D) photoinitiator; (E) a salt compound having a structural unit represented by the following formula (1); And (F) a photosensitive resin composition including a solvent, a black pixel partition layer prepared using the same, and a display device including the black pixel partition layer layer.
[Formula 1]

(In Formula 1, each substituent is as defined in the specification.)

Description

Photosensitive resin composition, black pixel barrier layer 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 black pixel partition wall layer 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 a resin film made of the composition due to outgassing.

Accordingly, research to develop a photosensitive resin composition for manufacturing a black pixel barrier layer capable of solving the above problem is ongoing.

One embodiment is to provide a photosensitive resin composition that can increase the life of the device through the reduction of outgas.

Another embodiment is to provide a black pixel partition wall layer manufactured using the photosensitive resin composition.

Another embodiment is to provide a display device including the black pixel barrier layer.

One embodiment is (A) an alkali-soluble resin; (B) a black colorant; (C) photopolymerizable monomer; (D) photoinitiator; (E) a salt compound having a structural unit represented by the following formula (1); And (F) It provides a photosensitive resin composition containing a solvent.

[Formula 1]

In Formula 1,

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,

Z ⁺ is a cation.

Wherein Z ⁺ is represented by N ⁺ R ¹ R ² R ³ R ⁴ (R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group) Can be.

X ¹ may be represented by the following Formula 2-1, and X ² and X ³ may each independently be represented by the following Formula 2-2.

[Formula 2-1]

[Formula 2-2]

A salt compound having a structural unit represented by Formula 1 may be represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1,

R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

The salt compound may include a substituted or unsubstituted acrylate group or carboxyl group at both ends.

The salt compound may include a functional group represented by Formula 3-1, a functional group represented by Formula 3-2, or a combination thereof at both ends.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

In Formula 3-1 and Formula 3-2,

R ¹¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

The salt compound may have a weight average molecular weight of 3,000 g/mol to 15,000 g/mol.

The salt compound may be included in an amount of 0.1% to 5% by weight based on the total amount of the photosensitive resin composition.

The salt compound may further include a structural unit represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

X ² and X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,

Y ¹ to Y ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

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 alkali-soluble resin may include a polymer having a structural unit represented by the following formula (5).

[Formula 5]

In Chemical Formula 5,

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.

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

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) alkali-soluble resin 1% by weight to 20% by weight; (B) 1% to 20% by weight of the black colorant; 1% to 15% by weight of the (C) photopolymerizable monomer; (D) 0.01% to 5% by weight of the photopolymerization initiator; (E) 0.1% to 5% by weight of a salt compound having a structural unit represented by Formula 1; And the residual amount of the (F) solvent.

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 black pixel partition wall layer manufactured using the photosensitive resin composition.

Another embodiment provides a display device including the black pixel barrier layer.

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 minimize outgassing by using a pigment dispersion containing a dispersant having excellent heat resistance, thereby improving life characteristics of an organic light emitting device.

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, unless otherwise defined, "*" refers to 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) a salt compound having a structural unit represented by the following formula (1); And (F) a solvent.

[Formula 1]

In Formula 1,

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,

Z ⁺ is a cation.

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 black out the planarization film and the 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 applied the dispersant structure constituting the pigment dispersion as a basic structure to the polyimide structure having high heat resistance in order to minimize the outgas that has the greatest effect on the life of the OLED device after a long study, while simultaneously applying the structure. By transforming it into a salt form, the outgas content could be minimized.

Hereinafter, each component will be described in detail.

(E) a salt compound having a structural unit represented by formula (1)

The photosensitive resin composition according to an embodiment includes a salt compound including a structural unit represented by Formula 1, and the salt compound may serve as a dispersant for dispersing a black colorant.

When the salt compound is used, outgas generated from the black photosensitive resin composition can be minimized by smoothly dispersing the black colorant, and further, the salt compound represented by Formula 1 has a polyimide structure as a basic structure. Since it has excellent heat resistance, it can further contribute to minimizing outgassing.

For example, in Formula 1, the cation Z ⁺ is N ⁺ R ¹ R ² R ³ R ⁴ (R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group).

For example, X ¹ may be represented by the following Formula 2-1, and X ² and X ³ may each independently be represented by the following Formula 2-2.

[Formula 2-1]

[Formula 2-2]

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

[Formula 1-1]

In Formula 1-1,

R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

For example, R ⁵ and R ⁶ may each independently be a C1 to C20 alkyl group substituted with a fluoro group, such as a trifluoromethyl group.

The salt compound may include a substituted or unsubstituted acrylate group or carboxyl group at both ends.

For example, the salt compound may include a functional group represented by Formula 3-1, a functional group represented by Formula 3-2, or a combination thereof at both ends.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

In Formula 3-1 and Formula 3-2,

R ¹¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.

The salt compound may further include a structural unit represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

X ² and X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,

Y ¹ to Y ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,

R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

For example, the salt compound may be represented by the following Formula D-1 or D-2, but is not limited thereto.

[Formula D-1]

[Formula D-2]

In Formulas D-1 and D-2,

Z ⁺ is a cation.

For example, the salt compound may have a weight average molecular weight of 3,000 g/mol to 15,000 g/mol.

The salt compound may be included in an amount of 0.1% to 5% by weight based on the total amount of the photosensitive resin composition. When the salt compound is included in the above range, it has excellent dispersibility with respect to the black colorant, can minimize outgassing, and can have excellent pattern formation.

(A) alkali-soluble resin

The alkali-soluble resin in the photosensitive resin composition according to an embodiment may include a polymer represented by Formula 5 below.

[Formula 5]

In Chemical Formula 5,

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.

The polymer represented by Chemical Formula 5 has excellent heat resistance, and when applied as a dispersion binder in a dispersion, the effect of reducing outgassing can be maximized.

For example, in Formula 5, X ¹ to X ³ may be as described above.

For example, Formula 5 may be represented by Formula 5-1 below.

[Chemical Formula 5-1]

In Formula 5-1,

R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

For example, R ⁵ and R ⁶ may each independently be a C1 to C20 alkyl group substituted with a fluoro group, such as a trifluoromethyl group.

For example, the polymer represented by Formula 5 may include a functional group represented by Formula 3-1 at both ends. By including the functional group at the terminal, heat resistance can be further improved.

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

The cardo-based binder resin may be represented by Formula 14 below.

[Formula 14]

In Chemical Formula 14,

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 14-1 to 14-11,

[Formula 14-1]

[Formula 14-2]

[Formula 14-3]

[Formula 14-4]

[Formula 14-5]

(In Chemical Formula 14-5,

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 14-6]

[Formula 14-7]

[Formula 14-8]

[Formula 14-9]

[Formula 14-10]

[Formula 14-11]

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 the following Chemical Formula 15 at at least one of both ends.

[Formula 15]

In Chemical Formula 15,

Z ³ may be represented by the following Chemical Formula 15-1 to Chemical Formula 15-7.

[Chemical Formula 15-1]

(In Formula 15-1, 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 15-2]

[Chemical Formula 15-3]

[Formula 15-4]

[Formula 15-5]

(In Formula 15-5, 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 15-6]

[Formula 15-7]

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.

If the binder resin according to an embodiment contains only the cardo-based binder resin alone, the phenomenon may be too rapid, and the taper characteristics may be greatly deteriorated (T-top profile observed). To prevent this, the alkali-soluble resin It is preferable to use the polymer represented by Chemical Formula 5 and the cardo-based binder resin together, and more preferably, the polymer represented by Chemical Formula 5 may be included in an amount higher than that of the cardo-based 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 1% to 20% by weight based on the total amount of 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 1% to 20% by weight, such as 2% to 15% by weight, based on a solid content based on the total amount of the photosensitive resin composition. When the solid content of 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 (6).

[Formula 6]

In Chemical Formula 6,

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 containing at least two or more functional groups represented by Formula 6 may include 2 to 6 functional groups represented by Formula 5. 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 6 may be a compound represented by Formula 7 or Formula 8.

[Formula 7]

[Formula 8]

In Formula 7 and Formula 8,

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 15% by weight, such as 3% to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, 　 curing occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, 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, for example, 0.1% to 3% by weight based on the total amount of 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.

(E) solvent

The solvent may be materials that have compatibility with the pigment dispersion, 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 balance, such as 30% to 80% by weight, such as 30% to 70% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability is excellent in manufacturing the black pixel barrier layer.

(F) 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 black pixel partition wall layer prepared by exposing, developing, and curing the above-described photosensitive resin composition.

A method of manufacturing the black pixel barrier layer 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 black pixel barrier layer.

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 salt compound)

Synthesis Example 1

While passing nitrogen through a 4-neck flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, 103 g of dimethylacetamide was added, and 0.046 mol of 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride was dissolved. Add 0.1 mol of pyridine and 0.023 mol of HEMA (2-hydroxy ethyl methacrylate). After the reaction is completed, 0.017 mol of SiDA ([Bis(3-aminopropyl)]polydimethylsiloxane) [KF-8010, Shin-Etsu Chemical Co., Ltd.] is added. After completion of the reaction (if not complete, raise the temperature), 0.017 mol of diaminobenzoic acid is added to dimethylacetamide to completely dissolve, and then dropping at 5° C. for 30 minutes. After dropping is completed, it reacts at 40°C for 2 hours. Thereafter, 0.052 mol of acetic anhydride was added and reacted at 60° C. for 5 hours to complete the imidation reaction. The reaction mixture was added to 6 times DIW to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and then dried under vacuum at a temperature of 30° C. for 24 hours. After dissolving the dried binder to 20 wt% in diethyleneglycol methyl ethyl ether, evaporate, and add diethyleneglycol methyl ethyl ether so that the moisture content is less than 500 ppm and the total solid content is 20 wt%, the following formula E- The polymer represented by 1 was synthesized. (Weight average molecular weight: 4,500 g/mol). Here, 0.017 mol of 2-(dimethylamino)ethyl acrylate was added dropwise for 30 minutes and stirred for 1 hour to finally prepare a salt compound represented by Formula E-1-1 below.

[Formula E-1]

[Formula E-1-1]

Synthesis Example 1-2

In Synthesis Example 1-1, except that o-Phenylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-2 was prepared.

[Formula E-1-2]

Synthesis Example 1-3

In Synthesis Example 1-1, except that p-phenylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-3 was prepared.

[Formula E-1-3]

Synthesis Example 1-4

In Synthesis Example 1-1, except that Tetramethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-1-4 was prepared.

[Formula E-1-4]

Synthesis Example 1-5

In Synthesis Example 1-1, except that Ethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-5 was prepared.

[Formula E-1-5]

Synthesis Example 1-6

In Synthesis Example 1-1, except that m-Xylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-6 was prepared.

[Formula E-1-6]

Synthesis Example 1-7

In Synthesis Example 1-1, except that p-Xylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-7 was prepared.

[Formula E-1-7]

Synthesis Example 1-8

In Synthesis Example 1-1, except that 2,2'-dimethyl-1,3-propanediamine was used instead of 2-(dimethylamino)ethyl acrylate, the salt compound represented by the following Formula E-1-8 was prepared in the same manner. Was prepared.

[Formula E-1-8]

Synthesis Example 1-9

In Synthesis Example 1-1, except that dibutylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-9 was prepared.

[Formula E-1-9]

Synthesis Example 1-10

In Synthesis Example 1-1, except that 1,3-phenyldiamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-1-10 was prepared.

[Formula E-1-10]

Synthesis Example 1-11

Except for using 1,2-phenyldiamine instead of 2-(dimethylamino)ethyl acrylate in Synthesis Example 1-1, a salt compound represented by the following Chemical Formula E-1-11 was prepared.

[Formula E-1-11]

Synthesis Example 1-12

A salt compound represented by Formula E-1-12 was prepared in the same manner as in Synthesis Example 1-1, except that Dimethylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate.

[Formula E-1-12]

Synthesis Example 1-13

In Synthesis Example 1-1, except that Tetramethylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-13 was prepared.

[Formula E-1-13]

Synthesis Example 1-14

In Synthesis Example 1-1, except that Hexamethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-14 was prepared.

[Formula E-1-14]

Synthesis Example 1-15

In Synthesis Example 1-1, except that hexamethyltriethylenetetramine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by Formula E-1-15 was prepared in the same manner.

[Formula E-1-15]

Synthesis Example 1-16

In Synthesis Example 1-1, except that Diethyletriamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-16 was prepared.

[Formula E-1-16]

Synthesis Example 1-17

In Synthesis Example 1-1, except that Triethylenetetramine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-1-17 was prepared.

[Formula E-1-17]

Synthesis Example 1-18

In Synthesis Example 1-1, except that Tetraethylenepentamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-1-18 was prepared.

[Formula E-1-18]

Synthesis Example 2-1

While passing nitrogen through a 4-neck flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, 103 g of dimethylacetamide was added, and 0.046 mol of 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride was dissolved. Add 0.1 mol of pyridine and 0.023 mol of aminobenzoic acid. After the reaction is completed, 0.017 mol of SiDA ([Bis(3-aminopropyl)]polydimethylsiloxane) [KF-8010, Shin-Etsu Chemical Co., Ltd.] is added. After completion of the reaction (if not complete, raise the temperature), 0.017 mol of diaminobenzoic acid is added to dissolve completely and dropping at 5° C. for 30 minutes. After dropping is completed, it reacts at 40 ℃ for 2 hours. Thereafter, 0.052 mol of acetic anhydride was added and reacted at 60° C. for 5 hours to complete the imidation reaction. The reaction mixture was added to 6 times DIW to generate a precipitate, and the precipitate was filtered and sufficiently washed with water, followed by drying under vacuum at a temperature of 30° C. for 24 hours. After dissolving the dried binder to 20 wt% in diethyleneglycol methyl ethyl ether, evaporate, and add diethyleneglycol methyl ethyl ether so that the moisture content is less than 500 ppm and the total solid content is 20 wt%, the formula E- The polymer represented by 2 was synthesized. (Weight average molecular weight: 5,200 g/mol) 0.017 mol of 2-(Dimethylamino)ethyl acrylate was added dropwise thereto for 30 minutes and stirred for 1 hour to finally prepare a chloride compound represented by Formula E-2-1 below.

[Formula E-2]

[Formula E-2-1]

Synthesis Example 2-2

Except for using o-Phenylenediamine instead of 2-(dimethylamino)ethyl acrylate in Synthesis Example 2-1, a salt compound represented by the following Chemical Formula E-2-2 was prepared.

[Formula E-2-2]

Synthesis Example 2-3

In Synthesis Example 2-1, except that p-phenylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-2-3 was prepared.

[Formula E-2-3]

Synthesis Example 2-4

In Synthesis Example 2-1, except that Tetramethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by Formula E-2-4 was prepared in the same manner.

[Formula E-2-4]

Synthesis Example 2-5

In Synthesis Example 2-1, except that Ethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-5 was prepared.

[Formula E-2-5]

Synthesis Example 2-6

In Synthesis Example 2-1, except that m-Xylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-6 was prepared.

[Formula E-2-6]

Synthesis Example 2-7

Except for using p-Xylenediamine instead of 2-(dimethylamino)ethyl acrylate in Synthesis Example 2-1, a salt compound represented by the following Chemical Formula E-2-7 was prepared.

[Formula E-2-7]

Synthesis Example 2-8

Except for using 2,2'-dimethyl-1,3-propanediamine instead of 2-(dimethylamino)ethyl acrylate in Synthesis Example 2-1, a salt compound represented by the following Formula E-2-8 was prepared. Was prepared.

[Formula E-2-8]

Synthesis Example 2-9

In Synthesis Example 2-1, except that dibutylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by Formula E-2-9 was prepared in the same manner.

[Formula E-2-9]

Synthesis Example 2-10

In Synthesis Example 2-1, except that 1,3-phenyldiamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-2-10 was prepared.

[Formula E-2-10]

Synthesis Example 2-11

In Synthesis Example 2-1, except that 1,2-phenyldiamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-2-11 was prepared.

[Formula E-2-11]

Synthesis Example 2-12

In Synthesis Example 2-1, except that Dimethylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-12 was prepared.

[Formula E-2-12]

Synthesis Example 2-13

In Synthesis Example 2-1, except that Tetramethylethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-13 was prepared.

[Formula E-2-13]

Synthesis Example 2-14

In Synthesis Example 2-1, except that Hexamethylenediamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-14 was prepared.

[Formula E-2-14]

Synthesis Example 2-15

In Synthesis Example 2-1, except that hexamethyltriethylenetetramine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by Formula E-2-15 was prepared in the same manner.

[Formula E-2-15]

Synthesis Example 2-16

In Synthesis Example 2-1, except that Diethyletriamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-16 was prepared.

[Formula E-2-16]

Synthesis Example 2-17

In Synthesis Example 2-1, except that Triethylenetetramine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Formula E-2-17 was prepared.

[Formula E-2-17]

Synthesis Example 2-18

In Synthesis Example 2-1, except that Tetraethylenepentamine was used instead of 2-(dimethylamino)ethyl acrylate, a salt compound represented by the following Chemical Formula E-2-18 was prepared.

[Formula E-2-18]

(Pigment dispersion preparation)

According to the composition shown in Table 1 below, a pigment dispersion liquid 1 to a pigment dispersion liquid 37 were prepared.

Pigment
(15% by weight) Salt compound
(3.6% by weight) Resin for dispersion
(2.3% by weight) menstruum
(79.1% by weight) Pigment dispersion 1 RBV* Formula E-1-1 Formula E-1 PGMEA** Pigment dispersion 2 RBV* Formula E-1-2 Formula E-1 PGMEA** Pigment dispersion 3 RBV* Formula E-1-3 Formula E-1 PGMEA** Pigment dispersion 4 RBV* Formula E-1-4 Formula E-1 PGMEA** Pigment dispersion 5 RBV* Formula E-1-5 Formula E-1 PGMEA** Pigment dispersion 6 RBV* Formula E-1-6 Formula E-1 PGMEA** Pigment dispersion 7 RBV* Formula E-1-7 Formula E-1 PGMEA** Pigment dispersion 8 RBV* Formula E-1-8 Formula E-1 PGMEA** Pigment dispersion 9 RBV* Formula E-1-9 Formula E-1 PGMEA** Pigment dispersion 10 RBV* Formula E-1-10 Formula E-1 PGMEA** Pigment dispersion 11 RBV* Formula E-1-11 Formula E-1 PGMEA** Pigment Dispersion 12 RBV* Formula E-1-12 Formula E-1 PGMEA** Pigment Dispersion 13 RBV* Formula E-1-13 Formula E-1 PGMEA** Pigment dispersion 14 RBV* Formula E-1-14 Formula E-1 PGMEA** Pigment dispersion 15 RBV* Formula E-1-15 Formula E-1 PGMEA** Pigment dispersion 16 RBV* Formula E-1-16 Formula E-1 PGMEA** Pigment dispersion 17 RBV* Formula E-1-17 Formula E-1 PGMEA** Pigment dispersion 18 RBV* Formula E-1-18 Formula E-1 PGMEA** Pigment dispersion 19 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 20 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment Dispersion 21 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 22 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 23 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 24 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 25 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 26 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment Dispersion 27 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 28 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 29 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 30 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 31 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 32 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 33 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 34 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 35 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 36 RBV* Formula E-1-1 Formula E-2 PGMEA** Pigment dispersion 37 RBV* DISPERBYK-102 (BYK company) PRIMAL™ HG-415 (DOW社) PGMEA**

* RBV: C.I. Red pigment 179, C.I. Blue pigment 15:6 and C.I. Mixture of violet pigment 29 (mixing ratio (w/w/w)=47/38/15)

** PGMEA: propylene glycol monomethyl ether acetate

(Production of photosensitive resin composition)

Example 1

After dissolving 0.5 g of a photopolymerization initiator (SPI-02, Samyang) in a solvent (PGMEA 49.4 g and 3-MBA (3-methylbenzoic acid) 8.07 g), the mixture was stirred at room temperature for 2 hours. Here, as a binder resin, 11.0 g of a polymer (A) represented by the above formula E-1, 4.5 g of a cardo-based resin (KBR-101, Kyungin Corporation) (B), and 2.5 g of a photopolymerizable monomer (DPHA, Japanese explosives), and 0.03 g of a fluorine-based surfactant (F-554, DIC) was added, and the mixture was stirred at room temperature for 1 hour. Here, 24.0 g of pigment dispersion 1 was added, and the mixture was stirred at room temperature for 1 hour, and then the entire solution was stirred for 2 hours. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

Examples 2 to 36 and Comparative Example 1

In Example 1, instead of the polymer represented by the pigment dispersion 1 and the formula E-1, a photosensitive resin composition was prepared with the configuration shown in Table 2 below.

Pigment dispersion
(24.0% by weight) Binder resin
(15.5% by weight) Photopolymerizable monomer
(2.5% by weight) Photopolymerization initiator
(0.5% by weight) menstruum
(57.47% by weight) Other additives
(0.03% by weight) (A) (B) Example 1 One Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 2 2 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 3 3 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 4 4 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 5 5 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 6 6 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 7 7 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 8 8 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 9 9 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 10 10 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 11 11 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 12 12 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 13 13 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 14 14 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 15 15 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 16 16 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 17 17 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 18 18 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 19 19 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 20 20 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 21 21 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 22 22 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 23 23 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 24 24 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 25 25 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 26 26 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 27 27 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 28 28 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 29 29 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 30 30 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 31 31 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 32 32 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 33 33 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 34 34 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 35 35 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Example 36 36 Formula E-2 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant Comparative Example 1 37 Formula E-1 Cardo resin DPHA SPI-02 PGMEA 3-MBA Fluorine-based surfactant

evaluation

The photosensitive resin composition according to Examples 1 to 36 and Comparative Example 1 was applied to 10cm*10cm clean glass, heated on a hot plate at 100°C for 1 minute in proxy type, and then heated again for 1 minute in contact type 1 A µm-thick photosensitive resin film was formed. The photosensitive resin film was cured at 250° C. for 1 hour under a nitrogen atmosphere. After cutting the cured glass into 1cm x 5cm, 7 sheets were put into the collection tube, outgas was collected at 250°C for 30 minutes, and then analyzed, and the results are shown in Table 3 below. Table 3 below shows the results of calculating and normalizing the total outgas area based on the comparative example.

Outgas content @ HS-GC/MS Total area Normalized Area (%) Example 1 1451762 60 Example 2 1572742 65 Example 3 1330782 55 Example 4 1209802 50 Example 5 1403370 58 Example 6 1379174 57 Example 7 1427566 59 Example 8 1233998 51 Example 9 1282390 53 Example 10 1185605 49 Example 11 1161409 48 Example 12 1209802 50 Example 13 1185605 49 Example 14 1354978 56 Example 15 1451762 60 Example 16 1354978 56 Example 17 1282390 53 Example 18 1427566 59 Example 19 1403370 58 Example 20 1233998 51 Example 21 1209802 50 Example 22 1451762 60 Example 23 1500154 62 Example 24 1475958 61 Example 25 1524350 63 Example 26 1427566 59 Example 27 1403370 58 Example 28 1306586 54 Example 29 1379174 57 Example 30 1354978 56 Example 31 1427566 59 Example 32 1403370 58 Example 33 1330782 55 Example 34 1209802 50 Example 35 1209802 50 Example 36 2177643 90 Comparative Example 1 2419603 100

From Table 3, it can be seen that the photosensitive resin composition containing the salt compound having the structural unit represented by Chemical Formula 1 has significantly better outgassing properties than the photosensitive resin composition not containing the salt polymer.

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 (17)

(A) alkali-soluble resin;
(B) a black colorant;
(C) photopolymerizable monomer;
(D) photoinitiator;
(E) a salt compound having a structural unit represented by the following formula (1); And
(F) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Formula 1,
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,
Z ⁺ is a cation.
The method of claim 1,
Wherein Z ⁺ is represented by N ⁺ R ¹ R ² R ³ R ⁴ (R ¹ to R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group) Photosensitive resin composition to become.
The method of claim 1,
X ¹ is represented by the following formula 2-1,
The X ² and X ³ are each independently a photosensitive resin composition represented by the following formula 2-2.
[Formula 2-1]

[Formula 2-2]

The method of claim 1,
The salt compound having a structural unit represented by Formula 1 is a photosensitive resin composition represented by Formula 1-1:
[Formula 1-1]

In Formula 1-1,
R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R ⁵ and R ⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.
The method of claim 1,
The salt compound is a photosensitive resin composition comprising a substituted or unsubstituted acrylate group or carboxyl group at both ends.
The method of claim 1,
The salt compound is a photosensitive resin composition comprising a functional group represented by Formula 3-1, a functional group represented by Formula 3-2, or a combination thereof at both ends:
[Chemical Formula 3-1]

[Chemical Formula 3-2]

In Formula 3-1 and Formula 3-2,
R ¹¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C6 to C20 arylene group.
The method of claim 1,
The salt compound further comprises a structural unit represented by the following formula (4):
[Formula 4]

In Chemical Formula 4,
X ² and X ³ are each independently a substituted or unsubstituted trivalent aromatic organic group,
Y ¹ to Y ³ are each independently a substituted or unsubstituted C1 to C20 alkylene group or a substituted or unsubstituted C6 to C20 arylene group,
R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.
The method of claim 1,
The salt compound is a photosensitive resin composition having a weight average molecular weight of 3,000 g / mol to 15,000 g / mol.
The method of claim 1,
The salt compound is a photosensitive resin composition containing 0.1% to 5% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The alkali-soluble resin is a photosensitive resin composition comprising a polymer having a structural unit represented by the following formula (5):
[Formula 5]

In Chemical Formula 5,
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.
The method of claim 10,
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.
delete 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 black pixel defining layer prepared using the photosensitive resin composition of any one of claims 1 to 13 and 15.
A display device comprising the black pixel barrier layer of claim 16.