KR102235263B1 - 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) a siloxane compound containing structural units represented by the following formulas (1) and (2); 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]

[Formula 2]

(In Chemical Formulas 1 and 2, 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, a color filter such as a color liquid crystal display requires a black pixel partition layer at the boundary between colored layers such as red, green, and blue in order to increase the display contrast or color development effect. , This black pixel partition wall layer is mainly formed of a photosensitive resin composition.

In particular, the pixel barrier layer used as a material for the display panel is mostly a transparent material, and has problems such as outdoor visibility, a viewing angle, and high reflection of external light.

Accordingly, in order to increase the optical density, a black pixel partition layer was also manufactured using a photosensitive resin composition using carbon black as a colorant, but in this case, the transmittance of light in the infrared region is low, making it difficult to patterning processes such as alignment. There is this. In addition, even if the patterning process is possible by using an organic black pigment instead of carbon black as a colorant, the transmittance to light in the UV region is low, and thus there is a problem such as a decrease in heat resistance due to a decrease in the light crosslinking rate, and inability to realize a step difference. Accordingly, the composition used for manufacturing the black pixel partition layer had to use an excessive amount of initiator for proper sensitivity, and thus the outgas characteristics were inevitably bad.

In addition, in order to disperse the black colorant, a dispersant having poor heat stability such as acrylic, urethane, and ester must be used, and there is also a problem in that it is difficult to improve outgas characteristics by the dispersant.

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 capable of significantly reducing outgassing than before while maintaining sensitivity and optical density at the same level as in the prior art by using a siloxane compound having excellent thermal stability.

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 siloxane compound containing a structural unit represented by the following formulas (1) and (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 a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² is a substituted or unsubstituted C6 to C20 aryl group,

R ³ is a C1 to C20 alkyl group unsubstituted or substituted with an amine group.

The R ³ may include a functional group represented by *-NR ⁴ R ⁵ (R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) at the terminal.

R ³ may include a linking group represented by *-NR ⁶ -* (R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group).

The siloxane compound may further include a structural unit represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group.

R ⁷ may be an unsubstituted C1 to C20 alkyl group.

The siloxane compound may include a functional group represented by the following formula (4) at either end of both ends, and a functional group represented by the following formula (5) at the other end.

[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,

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

The siloxane compound may be represented by the following Formula 1-1 or Formula 2-1.

[Formula 1-1]

[Formula 2-1]

The siloxane compound may be included in an amount of 0.01% to 5% by weight based on the total amount of the photosensitive resin composition.

The alkali-soluble resin may include an imide-amic acid polymer, a polybenzoxazole precursor, a polyimide precursor, or a combination thereof.

The alkali-soluble resin may include a structural unit represented by the following formula (6).

[Formula 6]

In Chemical Formula 6,

L ¹ is represented by the following formula (7),

L ² is a substituted or unsubstituted C1 to C20 alkylene group,

[Formula 7]

In Chemical Formula 7,

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

L ³ is a single bond or represented by the following formula (8),

[Formula 8]

In Chemical Formula 8,

L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C10 alkylene group,

n is an integer from 0 to 5.

R ¹¹ may be a hydrogen atom.

The alkali-soluble resin may include a functional group represented by the following formula (9) at both ends.

[Formula 9]

In Chemical Formula 9,

R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The alkali-soluble resin may further include a silicon diamine structural unit.

The silicone diamine structural unit may be represented by the following formula (10).

[Formula 10]

In Chemical Formula 10,

L ⁶ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹³ to R ¹⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

The alkali-soluble resin may have a weight average molecular weight of 5,000 g/mol to 20,000 g/mol.

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 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) 0.1% to 5% by weight of the photopolymerization initiator; 0.01% to 5% by weight of the (E) siloxane compound; 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 fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment provides a black pixel defining layer manufactured using the photosensitive resin composition.

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

The display device may be a liquid crystal display device (LCD) or 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 provide a black pixel partition wall layer having low-out gas characteristics by using a siloxane compound having excellent heat resistance.

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

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

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

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

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

Unless otherwise specified in the specification, "combination" means mixing or copolymerization.

Unless otherwise specified in the specification, the unsaturated bond includes not only multiple bonds between carbon-carbon atoms, but also other molecules such as carbonyl bonds and azo bonds.

Unless otherwise specified in the specification, the maximum transmittance and maximum absorbance range refers to a range within a range of 330 nm to 900 nm, and a range of less than 330 nm and more than 900 nm is not considered.

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

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 siloxane compound containing a structural unit represented by the following formulas (1) and (2); And (F) a solvent.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ² is a substituted or unsubstituted C6 to C20 aryl group,

R ³ is a C1 to C20 alkyl group unsubstituted or substituted with an amine group.

The pixel barrier layer, which is currently applied to a display device, is a transparent material and has problems such as outdoor visibility, a viewing angle, and high reflection of external light. In order to compensate for these problems, there is a growing need in the industry for a pixel barrier layer with improved optical properties. Specifically, there is a growing demand for a black pixel barrier layer with improved outgas characteristics while retaining the advantages of the existing black pixel barrier layer such as sensitivity and optical density.

In the conventional case, carbon black (inorganic black) or organic black was used to sufficiently use a light source, and an excessive amount of initiator had to be used for proper sensitivity. As a result, it was an inevitable phenomenon that the outgas characteristics were deteriorated. In addition, it has been more difficult to achieve improvement in outgassing properties by using dispersants such as acrylic, urethane, and esters having poor thermal stability in order to disperse carbon black or organic black pigment used as a black colorant. In order to solve this problem, by developing and using a silicone-based dispersant with excellent thermal stability, a photosensitive resin composition capable of manufacturing a black pixel partition layer having low-out gas characteristics while maintaining the sensitivity and optical density at the same level as the conventional one was developed. It came to the following.

Hereinafter, each component will be described in detail.

(E) siloxane compound

The photosensitive resin composition according to an embodiment includes a siloxane compound including structural units represented by Chemical Formulas 1 and 2, and the siloxane compound may serve as a dispersant for dispersing a black colorant.

The photosensitive resin composition for the black pixel partition layer often uses a black pigment as a black colorant, and a dispersant must be used to disperse the black pigment.Black colorants such as carbon black, organic black, and mixed color pigments are acrylic dispersants, urethane-based Dispersing agents or ester-based dispersants are well dispersed, and these dispersants are mainly used. However, the dispersant has poor thermal stability, and there is a problem in that an excessive amount of outgas is generated.

However, according to one embodiment, the siloxane compound containing the structural units represented by Chemical Formulas 1 and 2 has excellent thermal stability and excellent dispersing power for a black colorant. By using this as a dispersant, the effect of reducing outgassing is achieved. Can be achieved.

For example, the R ³ may include a functional group represented by *-NR ⁴ R ⁵ (R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) at the terminal.

For example, R ³ may include a linking group represented by *-NR ⁶ -* (R ⁶ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group).

Since R ^{3 includes} a functional group represented by *-NR ⁴ R ^{5 and a linking group represented by *-NR 6} -*, the dispersibility of the black colorant may be improved even with a small content.

For example, R ³ may be represented by the following Formula A, but is not limited thereto.

[Formula A]

In Formula A,

R ⁴ to R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L'and L'' are each independently a substituted or unsubstituted C1 to C10 alkylene group.

The siloxane compound may further include a structural unit represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group.

For example, R ⁷ may be an unsubstituted C1 to C20 alkyl group.

When the siloxane compound contains all of the structural units represented by Chemical Formulas 1, 2, and 3, the outgas reduction effect becomes more excellent.

The siloxane compound may include a functional group represented by the following formula (4) at either end of both ends, and a functional group represented by the following formula (5) at the other end.

[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,

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

For example, R ⁸ to R ¹⁰ may each independently be a substituted or unsubstituted C1 to C20 alkyl group.

For example, the siloxane compound may be represented by the following Formula 1-1 or Formula 2-1.

[Formula 1-1]

[Formula 2-1]

The siloxane compound may have a weight average molecular weight of 1,000 g/mol to 30,000 g/mol.

The siloxane compound may be included in an amount of 0.01% to 5% by weight, for example, 0.05% to 3% by weight based on the total amount of the photosensitive resin composition. When the siloxane compound is included in the above content range, it is possible to prevent a decrease in sensitivity and optical density while maximizing an effect of reducing outgassing at the same time.

(A) alkali-soluble resin

The alkali-soluble resin included in the photosensitive resin composition according to one embodiment is a heat-resistant resin, and may include, for example, an imide-amic acid polymer, a polybenzoxazole precursor, a polyimide precursor, or a combination thereof, but is limited thereto. It is not.

For example, the alkali-soluble resin may include a structural unit represented by the following formula (6).

[Formula 6]

In Chemical Formula 6,

L ¹ is represented by the following formula (7),

L ² is a substituted or unsubstituted C1 to C20 alkylene group,

[Formula 7]

In Chemical Formula 7,

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

L ³ is a single bond or represented by the following formula (8),

[Formula 8]

In Chemical Formula 8,

L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C10 alkylene group,

n is an integer from 0 to 5.

Since the alkali-soluble resin constituting the photosensitive resin composition according to an embodiment includes the structural unit represented by Chemical Formula 6, it has excellent heat resistance and can improve sensitivity and outgas characteristics (outgas reduction effect). . In particular, the linking group represented by Chemical Formula 7 facilitates optical crosslinking, and thus can play a large role in reducing outgassing, and has excellent sensitivity.

For example, R ¹¹ may be a hydrogen atom. When R ¹¹ is a hydrogen atom, the alkali-soluble resin has an acrylic group in its structure, and thus it may be more effective in reducing outgassing.

The alkali-soluble resin may include a functional group represented by the following formula (9) at both ends.

[Formula 9]

In Chemical Formula 9,

R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, R ¹² may be a substituted or unsubstituted C1 to C10 alkyl group. When R ¹² is an alkyl group, the alkali-soluble resin has an acrylic group substituted with an alkyl group such as a methacrylic group at both ends, and thus it may be more effective in reducing outgassing.

That is, when the alkali-soluble resin has an acrylic group (without substitution of an alkyl group, etc.) in a structure other than the terminal, and has a methacrylic group (with an alkyl group, etc. substituted) at both ends, the outgas characteristics are greatly improved (outgas reduction). ).

The alkali-soluble resin may further include a silicon diamine structural unit.

When the alkali-soluble resin further includes the silicone diamine structural unit, the taper angle of the pattern is lowered, thereby helping to improve patternability and processability.

The silicone diamine structural unit may be represented by the following formula (10).

[Formula 10]

In Chemical Formula 10,

L ⁶ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R ¹³ to R ¹⁶ are each independently a substituted or unsubstituted C1 to C20 alkyl group.

For example, the alkali-soluble resin may have a weight average molecular weight of 5,000 g/mol to 20,000 g/mol, for example, 6,000 g/mol to 10,000 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 photo-binding efficiency and heat resistance can be greatly increased. 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 content of the pigment may be included in 5% by weight to 30% by weight, such as 8% by weight to 15% by weight, such as 8% by weight to 12% 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 may be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

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

The photopolymerizable monomer 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, pentaerythritoldi(meth)acrylate, penta Erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) Acrylate, tris(meth)acryloyloxyethylphosphate, novolacepoxy(meth)acrylate　, or a combination thereof.

For example, commercially available products of the photopolymerizable monomer are 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 photopolymerization initiator may have a maximum absorbance at 350 nm to 400 nm. For example, the photopolymerization initiator may have a maximum absorbance at 360 nm to 390 nm.

When preparing the photosensitive resin composition, when the photopolymerization initiator is used together with the aforementioned black colorant, internal curing is efficiently performed while showing black color, thereby maximizing the process margin, and also improving the photocuring efficiency.

As the photoinitiator, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, an acetophenone compound, or a combination thereof may be used.

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

Examples of the thioxanthone-based compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- And chlorothioxanthone.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4 -Bis(trichloromethyl)-6-piperonyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, 2-[4 -(4-ethylphenyl)-phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, etc. are mentioned.

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

For example, the photopolymerization initiator having a maximum absorbance at 350 nm to 400 nm may be an oxime compound. For example, the photopolymerization initiator having a maximum absorbance at 350 nm to 400 nm may include an O-acyloxime compound, but is not limited thereto.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,4,6-trimethybenzoyl)phenylphosphine oxide, etc. are mentioned. .

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

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

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.1% to 5% by weight, such as 0.5% to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, curing occurs sufficiently during exposure in the pattern formation process to obtain excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, excellent resolution and adhesion, and an unreacted initiator It is possible to prevent the decrease in transmittance due to.

(E) solvent

The solvent may be materials that have compatibility with the black colorant, the photopolymerization initiator, the photopolymerizable monomer, the siloxane compound, and the alkali-soluble resin, 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 (EDM); Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol 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; Alkoxyacetic acid alkyl esters such as methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, and ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, and 3-ethoxy methyl propionate; 2-oxypropionic acid alkyl esters such as 2-oxypropionate methyl, 2-oxypropionate ethyl, and 2-oxypropionate propyl; 2-alkoxypropionic acid alkyl esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, and 2-ethoxy methyl propionate; 2-oxy-2-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-methylpropionic acid 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, and the like, and 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 And high boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among these, in consideration of compatibility and reactivity, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether and diethylene glycol ethyl methyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate may 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 fluorine-based 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, such as a fluorine-based surfactant, to improve coating properties and prevent defects from being generated, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; ^{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; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The fluorine-based surfactant may be used in an amount of 0.001 parts by weight 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.

As the photosensitive resin composition according to an embodiment has the above-described composition, the near-infrared transmittance may be 40% or more, for example, 90% or more, and thus the exposure process may be easily performed. In general, the near-infrared transmittance must have a certain level, for example, a value of about 40% or more to align the alignment, so that the exposure process can be easily performed and patterning is possible (if the value is about 90% or more, the exposure process becomes very easy). The near-infrared transmittance becomes one of the criteria for determining whether or not the photosensitive resin composition can be patterned.

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 IZO substrate subjected to a predetermined pretreatment by using a spin or slit coating method, a roll coating method, a screen printing method, or an applicator method, 70 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 (using a 365 nm sensor) or less 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 a liquid crystal display device (LCD) or 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.

(Example)

(Synthesis of alkali-soluble resin)

Synthesis Example 1

While passing nitrogen through a 4-neck flask equipped with a stirrer, temperature controller, nitrogen gas injection device, and cooler, add 86.6 g of N-methyl-2-pyrrolidone (NMP) and 4,4'-hexafluoroisopropyl 12.3 g of leaden diphthalic anhydride (6-FDA) was added and dissolved. When the solid was completely dissolved, 1.52 g of diaminobenzoic acid was added and stirred at room temperature for 1 hour, and then 1.75 g of silicon diamine (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. After cooling the temperature in the reactor to room temperature, 0.33 g of 2-hydroethyl methacrylate (HEMA) was added, stirred for 6 hours, and then pyridine was removed through a distillation process, and 1.28 g of glycidyl acrylate and toluene sulfonic solution Into the seed 0.2g was stirred for 3 hours. Thereafter, the reaction mixture was added to water to generate a precipitate, the precipitate was filtered and sufficiently washed with water, and then dried under vacuum at 50 °C for 24 hours or more to prepare a polymer represented by the following formula A-1. The weight average molecular weight of the synthesized polymer determined by GPC method in terms of standard polystyrene was 6,500 g/mol, and the dispersion degree was 1.85.

[Formula A-1]

Synthesis Example 2

While passing nitrogen through a 4-neck flask equipped with a stirrer, temperature controller, nitrogen gas injection device, and cooler, 86.6 g of N-methyl-2-pyrrolidone (NMP) was added, and 4,4'-hexafluoroiso 12.3 g of propylidene diphthalic anhydride (6-FDA) was added and dissolved. When the solid was completely dissolved, 1.52 g of diaminobenzoic acid was added, stirred at room temperature for 1 hour, and then 1.75 g of silicon diamine (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 (Ac2O) were added, followed by stirring for 3 hours. After cooling the temperature in the reactor to room temperature, 0.33 g of 2-hydroethyl methacrylate (HEMA) was added and stirred for 6 hours, and the reaction mixture was added to water to generate a precipitate, and the precipitate was filtered and sufficiently washed with water. Thereafter, drying was performed under vacuum at a temperature of 50 °C for 24 hours or more to prepare a polymer represented by the following formula A-2. The weight average molecular weight of the synthesized polymer determined by GPC method in terms of standard polystyrene was 6,400 g/mol, and the dispersion degree was 1.82.

[Formula A-2]

Synthesis Example 3

A polymer represented by the following formula (A-3) was prepared in the same manner as in Synthesis Example 1, except that silicone diamine (PAM-E, Shin-Etsu Chemical Co., Ltd.) was not added. The weight average molecular weight of the synthesized polymer determined by GPC method in terms of standard polystyrene was 6,900 g/mol, and the dispersion degree was 1.81.

[Formula A-3]

(Synthesis of siloxane compounds)

Synthesis Example 4

9.1 g of dimethoxymethylphenylsilane, 10.3 g of aminoethylaminopropyldimethoxymethylsilane, 5.2 g of methoxytrimethylsilane, 24.6 g of PGMEA was stirred at room temperature, and an aqueous nitric acid solution in which 0.023 g of nitric acid was dissolved in 2.3 g of water was added over 10 minutes. After stirring for 1 hour, the temperature was raised to 110° C., and stirred for 4 hours to obtain a siloxane compound (weight average molecular weight: 12,000 g/mol) represented by the following formula 1-1.

[Formula 1-1]

Synthesis Example 5

A nitric acid solution in which 0.025 g of nitric acid is dissolved in 2.5 g of water while stirring dimethoxymethylphenylsilane 9.1 g, dimethoxymethyloctylsilane 10.9 g, aminoethylaminopropyl dimethoxy methylsilane 10.3 g methoxytrimethylsilane 5.2 g PGMEA 35.5 g at room temperature while stirring Was added over 10 minutes. After stirring for 1 hour, the temperature was raised to 110° C., and stirred for 4 hours to obtain a siloxane compound (weight average molecular weight: 11,500 g/mol) represented by the following formula 2-1.

[Formula 2-1]

(Production of photosensitive resin composition)

Examples 1 to 5

In the composition shown in Table 1 below, after dissolving a photopolymerization initiator in a solvent, the mixture was stirred at room temperature for 2 hours. To this, an alkali-soluble resin and a photopolymerizable monomer were added, followed by stirring at room temperature for 1 hour. Here, a fluorine-based surfactant and a black colorant dispersed using the siloxane compound prepared in Synthesis Example were 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.

Comparative Example 1 and Comparative Example 2

A photosensitive resin composition was prepared in the same manner as in Examples, except that the siloxane compound prepared in Synthesis Example was not used, and the dispersant described in Table 1 below was used as other additives.

(Unit: g) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Alkali-soluble resin A-1 15 15 - - - 15 15 A-2 - - 15 15 - - - A-3 - - - - 15 - - Black colorant 40 40 40 40 40 40 40 Photopolymerizable monomer 5 5 5 5 5 5 5 Photopolymerization initiator D-1 0.4 0.4 0.4 0.4 0.4 0.4 0.4 D-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Siloxane compounds E-1 0.1 - 0.1 - 0.1 - - E-2 - 0.1 - 0.1 - - - menstruum F-1 29 29 29 29 29 29 29 F-2 10.2 10.2 10.2 10.2 10.2 10.2 10.2 Other additives G-1 0.03 0.03 0.03 0.03 0.03 0.03 0.03 G-2 - - - - - 0.1 - G-3 - - - - - - 0.1

(A) binder resin

(A-1) Binder resin prepared in Synthesis Example 1

(A-2) Binder resin prepared in Synthesis Example 2

(A-3) Binder resin prepared in Synthesis Example 3

(B) black colorant

RGB mixed color black pigment mill base (CI-IM-R176, SAKATA; RGB solid content 30% by weight)

(C) photopolymerizable monomer

Dipentaerythritol hexa(meth)acrylate (DPHA, Japanese explosives)

(D) photopolymerization initiator

(D-1) oxime initiator (NCI-831, ADEKA)

(D-2) Oxime initiator (SPI-02, Samyang)

(E) siloxane compound

(E-1) siloxane compound prepared in Synthesis Example 4

(E-2) siloxane compound prepared in Synthesis Example 5

(F) solvent

(F-1) Propylene glycol monomethyl ether acetate (Sigma-Aldrich)

(F-2) Diethylene glycol ethylmethyl ether (Sigma-Aldrich)

(G) other additives

(G-1) Fluorine-based surfactant (F-554, DIC company)

(G-2) Dispersant (EFKA PA 4400, BASF)

(G-3) Dispersant (EFKA PU 4010, BASF)

Evaluation 1: Sensitivity

After coating the photosensitive resin composition according to Examples 1 to 5, Comparative Example 1 and Comparative Example 2 on a glass substrate using a spin coater from Mikasa, it was heated on a hot plate at 100° C. for 1 minute to a thickness of 1 μm. A coating film of was formed. After exposing the substrate coated with the coating film using a Ushio exposure machine (UX-1200SM) using a mask with patterns of various sizes, changing the exposure amount, and developing it with a 2.38% TMAH solution at room temperature for 60 seconds. , After removing the exposed part by dissolving, it was washed with pure water for 30 seconds to form a pattern. As for the sensitivity, the energy at which a 20 µm hole was formed was confirmed based on the size of the 20 µm hole pattern measured using Hitachi's S-9260, and the sensitivity measurement results are shown in Table 2 below.

Evaluation 2: optical density

The photosensitive resin compositions of Examples 1 to 5, Comparative Examples 1 and 2 were coated, exposed, developed, and post-baked, and the patterned specimens were measured for optical density per 1 μm using an OD meter, The results are shown in Table 2 below.

Assessment 3: Outgas

From the photosensitive resin compositions of Examples 1 to 5, Comparative Examples 1 and 2, coating, exposure, development, and post-baking were completed, and the patterned specimen was cut into a size of 1 cm x 5 cm, and then placed in a collection tube 230 The gas generated for 30 minutes at °C was collected and the sum of the total area of the gas detected using GC-MS was confirmed, and is shown in Table 2 below.

Evaluation 4: taper angle

After curing the wafer and glass measured in Evaluation 3 at 250° C. for 1 hour in a nitrogen atmosphere, the taper angle was measured with Hitachi's S-4300 (FE-SEM equipment), and the results are shown in Table 2 below. Shown in.

Sensitivity (mJ/㎠) OD(/um) Outgas Taper angle (°) Example 1 60 1.2 248526 22 Example 2 60 1.2 205426 24 Example 3 80 1.2 584126 24 Example 4 80 1.2 518634 27 Example 5 60 1.2 251274 42 Comparative Example 1 60 1.2 2923840 32 Comparative Example 2 60 1.2 2258590 37

From Table 2, it can be seen that when using the siloxane compound containing the structural units represented by Chemical Formulas 1 and 2, it is possible to achieve an effect of reducing outgassing while preventing a decrease in sensitivity and optical density. Furthermore, it can be seen that when an alkali-soluble resin containing the structural unit represented by Formula 6 is used, the optical properties can be maintained at the same level as in the prior art, and the low-out gas properties can be secured. In addition, it can be seen that when the alkali-soluble resin further includes a silicone diamine structural unit, the taper angle may be lowered, thereby contributing to improvement in patternability and processability.

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 and non-limiting in all respects.

Claims (20)

(A) alkali-soluble resin;
(B) a black colorant;
(C) photopolymerizable monomer;
(D) photoinitiator;
(E) a siloxane compound containing structural units represented by the following formulas (1) and (2); And
(F) solvent
Photosensitive resin composition comprising:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ² is a substituted or unsubstituted C6 to C20 aryl group,
R ³ is a C1 to C20 alkyl group unsubstituted or substituted with an amine group.
The method of claim 1,
The photosensitive resin composition comprising a functional group represented by *-NR ⁴ R ⁵ (R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group) at the ^{end of R 3.}
The method of claim 1,
The siloxane compound is a photosensitive resin composition further comprising a structural unit represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group.
The method of claim 1,
The siloxane compound includes a functional group represented by the following formula (4) at either end of both ends, and the photosensitive resin composition comprising a functional group represented by the following formula (5) at the other end:
[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,
R ⁸ 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 siloxane compound is a photosensitive resin composition represented by the following Formula 1-1 or Formula 2-1.
[Formula 1-1]

[Formula 2-1]

The method of claim 1,
The siloxane compound is a photosensitive resin composition having a weight average molecular weight of 1,000 g / mol to 30,000 g / mol.
The method of claim 1,
The siloxane compound is a photosensitive resin composition contained in an amount of 0.01% to 5% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The alkali-soluble resin is an imide-amic acid polymer, a polybenzoxazole precursor, a polyimide precursor, or a photosensitive resin composition comprising a combination thereof.
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 (6):
[Formula 6]

In Chemical Formula 6,
L ¹ is represented by the following formula (7),
L ² is a substituted or unsubstituted C1 to C20 alkylene group,
[Formula 7]

In Chemical Formula 7,
R ¹¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ³ is a single bond or represented by the following formula (8),
[Formula 8]

In Chemical Formula 8,
L ⁴ and L ⁵ are each independently a substituted or unsubstituted C1 to C10 alkylene group,
n is an integer from 0 to 5.
The method of claim 9,
The alkali-soluble resin is a photosensitive resin composition comprising a functional group represented by the following formula (9) at both ends:
[Formula 9]

In Chemical Formula 9,
R ¹² is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
The method of claim 9,
The alkali-soluble resin is a photosensitive resin composition further comprising a silicone diamine structural unit.
The method of claim 11,
The silicone diamine structural unit is a photosensitive resin composition represented by the following formula (10):
[Formula 10]

In Chemical Formula 10,
L ⁶ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ¹³ to R ¹⁶ 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 having a weight average molecular weight of 5,000 g / mol to 20,000 g / mol.
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 the photosensitive resin composition
(A) 1 to 20% by weight of the alkali-soluble resin;
(B) 1% to 20% by weight of the black colorant;
1% to 15% by weight of the (C) photopolymerizable monomer;
(D) 0.1% to 5% by weight of the photopolymerization initiator;
0.01 to 5% by weight of the (E) siloxane compound; And
The residual amount of the (F) solvent
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 fluorine-based 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 17.
A display device comprising the black pixel barrier layer of claim 18.
The method of claim 19,
The display device is a liquid crystal display device (LCD) or an organic light emitting device (OLED).