KR102154679B1 - Photosensitive resin composition, photosensitive resin layer using the same and display device - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)A photosensitive resin composition comprising an alkali-soluble resin containing a polymer having a structural unit represented by the following Chemical Formula 1, a photosensitive resin film prepared using the same, and a display device including the photosensitive resin film are provided.
[Formula 1]

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

Description

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

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

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

In particular, a photosensitive resin film such as a pixel partition layer used as a material for a display panel must maintain a taper angle within a certain angular range in order to have fairness and device reliability. In addition, a black pigment that absorbs light in the visible light region, such as carbon black, RGB mixed black pigment, perylene-based compound, cobalt oxide, and lactam-based organic black pigment, should be used for shading properties.

Organic light-emitting devices are in the spotlight as a next-generation display because they have advantages of self-luminescence, wide viewing angles, and thin-film types, but have a short lifespan due to rapid aging of the devices due to moisture. In order to overcome this, methods to prevent moisture and outgassing from the manufacturing process and chemical substances used in the manufacturing process are continuously developed.

In addition, the photosensitive resin composition forms a fine structure (photosensitive resin film) such as an insulating film and a planarization film in the organic light emitting device, and there is a problem in that the pattern of the photosensitive resin film collapses during thermal curing.

One embodiment is to provide a photosensitive resin composition that hardly generates scum and residue during pattern formation, has an excellent development margin, and can maintain a taper angle within a predetermined range.

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

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

One embodiment provides a photosensitive resin composition comprising an alkali-soluble resin, a colorant, a photopolymerizable monomer, a photoinitiator, and a solvent including a polymer having a structural unit represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is a substituted or unsubstituted C1 to C20 alicyclic organic group or a substituted or unsubstituted C6 to C20 aromatic organic group,

Y is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

Z is a linking group derived from Formula 2 below,

m and n are molar contents, m is 30 to 80 mol%, n is 20 mol% to 70 mol%,

[Formula 2]

(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d

In Chemical Formula 2,

R ¹ to R ⁶ are each independently a hydrogen atom, an amine group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted A substituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, *-(C=O)R ⁷ (where R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group), (meth)acrylate group, (meth)acrylic A royloxy group or a combination thereof,

However, at least one of the R ¹ to R ⁶ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a C1 to C20 alkyl group substituted with a (meth) acrylate group or a (meth) acryloyloxy group at the terminal ego,

0<a<1, 0≤b<1, 0≤c<1, 0≤d<1, and a+b+c+d=1.

Z may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

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

R ⁸ to R ¹⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group,

However, at least one of the R ⁸ to R ¹⁷ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a (meth) acrylate group or a (meth) acryloyloxy group substituted at the terminal C1 to C20 It is an alkyl group.

The R ⁸ , R ⁹ and R ¹⁵ to R ¹⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group, and R ¹⁰ and R ¹⁴ are each independently a substituted or unsubstituted C6 to C20 aryl group, and the R ¹¹ and R ¹³ are each independently a substituted or unsubstituted C1 to C20 alkoxy group, and R ¹² is a (meth)acrylate group, a (meth)acryloyloxy group, or a (meth)acrylate group or ( The meth)acryloyloxy group may be a substituted C1 to C20 alkyl group.

The m and n may have a molar ratio of 1.2:1 to 2:1. Preferably, it may have a molar ratio of 1.4:1 to 1.6:1.

The polymer may have a weight average molecular weight of 1,000 g/mol to 20,000 g/mol.

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

The photosensitive resin composition may comprise 1% to 20% by weight of the alkali-soluble resin based on the total amount of the photosensitive resin composition; 5% to 15% by weight of the photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator; 1% to 20% by weight of the colorant; And the remaining amount of the solvent.

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

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

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

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

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

The photosensitive resin composition according to an embodiment includes a copolymer prepared by imidizing a polyimide structural unit and a polysiloxane structural unit with each other as an alkali-soluble resin, so that there is no scum and residue during pattern formation, excellent developability, and high temperature. It is possible to maintain a certain level of taper angle even during thermal curing of, so it is easy to adjust the taper characteristics, and ultimately, it is possible to provide an organic light emitting device having excellent optical characteristics.

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-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 defined herein, "combination" means mixing or copolymerization. In addition, "copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

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

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

In the present specification, unless otherwise defined, "*" means a part connected to the same or different atoms or chemical formulas.

The photosensitive resin composition according to an embodiment includes an alkali-soluble resin including a polymer having a structural unit represented by Formula 1 below, a colorant, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

[Formula 1]

In Formula 1,

X is a substituted or unsubstituted C1 to C20 alicyclic organic group or a substituted or unsubstituted C6 to C20 aromatic organic group,

Y is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,

Z is a linking group derived from Formula 2 below,

m and n are molar contents, m is 30 to 80 mol%, n is 20 mol% to 70 mol%,

[Formula 2]

(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d

In Chemical Formula 2,

R ¹ to R ⁶ are each independently a hydrogen atom, an amine group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted A substituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, *-(C=O)R ⁷ (Where R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group), (meth)acrylate group, (meth)acrylic A royloxy group or a combination thereof,

However, at least one of the R ¹ to R ⁶ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a C1 to C20 alkyl group substituted with a (meth) acrylate group or a (meth) acryloyloxy group at the terminal ego,

0<a<1, 0≤b<1, 0≤c<1, 0≤d<1, and a+b+c+d=1.

Hereinafter, each component will be described in detail.

(A) alkali-soluble resin

The photosensitive resin composition according to an embodiment includes a polymer having a structural unit represented by Formula 1 as an alkali-soluble resin. The structural unit represented by Formula 1 can be obtained by imidizing a siloxane copolymer obtained by hydrolysis and condensation reaction of the compound represented by Formula 2 and a polyimide having excellent heat resistance. In particular, by introducing T-type and D-type siloxane structures to improve flow characteristics, the taper angle can be easily adjusted to a desired level (within a specific range) according to the molar ratio of the siloxane copolymer and polyimide. In addition, the compound represented by Formula 2 must have a (meth)acrylate group or a (meth)acryloyloxy group as a substituent, and the alkali-soluble resin has excellent development margin for an alkali developer, and has a pattern of several μm. Formation is possible, and scum or residue hardly occurs during pattern formation.

For example, in Formula 1, Z may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

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

R ⁸ to R ¹⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group,

However, at least one of the R ⁸ to R ¹⁷ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a (meth) acrylate group or a (meth) acryloyloxy group substituted at the terminal C1 to C20 It is an alkyl group.

For example, in Formula 3, R ⁸ , R ⁹ and R ¹⁵ to R ¹⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group, and R ¹⁰ and R ¹⁴ are each independently substituted or unsubstituted C6 to C20 An aryl group, R ¹¹ and R ¹³ are each independently a substituted or unsubstituted C1 to C20 alkoxy group, and R ¹² is a (meth)acrylate group, a (meth)acryloyloxy group, or a (meth)acrylate at the terminal A group or a (meth)acryloyloxy group may be a substituted C1 to C20 alkyl group. When the siloxane copolymer constituting the alkali-soluble resin according to one embodiment has such a configuration, the taper characteristics can be adjusted to suit the applicable application while maintaining the dissolution rate similar, thereby improving optical characteristics.

In Formula 1, m and n may have a molar ratio of 1: 0.5 to 1: 2, or a molar ratio of 1.2: 1 to 2: 1, or a molar ratio of 1.4: 1 to 1.6: 1. When the polyimide and siloxane copolymer have such a molar ratio, it becomes easier to control the taper characteristics, it becomes easier to implement a step of 1 μm level, and the crosslinking property of the alkali-soluble resin becomes more excellent.

The polymer may have a weight average molecular weight of 1,000 g/mol to 20,000 g/mol, for example, 1,000 g/mol to 10,000 g/mol. When the weight average molecular weight of the polymer is within the above range, it has excellent pattern formation, and the prepared photosensitive resin film may have excellent mechanical and thermal properties.

The polymer may have an unsaturated double bond at at least one end, such as at both ends. The unsaturated double bond may exist in the middle of the chain of the alkali-soluble resin in addition to the terminal of the alkali-soluble resin. The unsaturated double bond at the end (and/or the middle of the chain) acts as a crosslinkable functional group, thereby improving crosslinking properties of the alkali-soluble resin. That is, in order to impart crosslinking properties of the alkali-soluble resin itself by exposure, a monomer capable of crosslinking by a photopolymerization initiator to be described later is introduced into the terminal group (and/or in the middle of the chain) of the main structure. The composition can be implemented.

The photosensitive resin composition according to an embodiment may further include an acrylic binder resin and/or a cardo-based binder resin as an alkali-soluble resin in addition to the polymer including the structural unit represented by Formula 1 so as to have excellent melting properties. have.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one acrylic repeating unit.

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

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

The second ethylenically unsaturated monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethylether; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth)acrylate and phenyl (meth)acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth)acrylate and 2-dimethylaminoethyl (meth)acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth)acrylate; Vinyl cyanide compounds such as (meth)acrylonitrile; Unsaturated amide compounds such as (meth)acrylamide; And the like, and these may be used alone or in combination of two or more.

Specific examples of the acrylic binder resin include (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/benzyl methacrylate/2-hydroxyethyl meth Acrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more. have.

The weight average molecular weight of the acrylic binder resin may be 5,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition are excellent, the viscosity is appropriate, and adhesion with the substrate is excellent when manufacturing a color filter.

The acid value of the acrylic binder resin may be 80 mgKOH/g to 130 mgKOH/g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The cardo-based binder resin may be represented by Formula 11.

[Formula 11]

In Formula 11,

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 (where 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 11-1 to 11-11,

[Chemical Formula 11-1]

[Formula 11-2]

[Chemical Formula 11-3]

[Formula 11-4]

[Formula 11-5]

(In Formula 11-5,

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 11-6]

[Formula 11-7]

[Formula 11-8]

[Formula 11-9]

[Formula 11-10]

[Formula 11-11]

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 is formed without residues when the light shielding layer is manufactured, there is no loss of film thickness during development, and a good pattern can be obtained.

The cardo-based binder resin may include a functional group represented by Formula 12 below at at least one of both ends.

[Formula 12]

In Formula 12,

Z ³ may be represented by the following Chemical Formula 12-1 to Chemical Formula 12-7.

[Chemical Formula 12-1]

(In Formula 12-1, 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 12-2]

[Chemical Formula 12-3]

[Chemical Formula 12-4]

[Formula 12-5]

(In Formula 12-5, 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.)

[Chemical Formula 12-6]

[Chemical Formula 12-7]

The cardo-based binder resin includes, 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 acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; Solvent compounds such as propylene glycol methyl ethyl 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.

When the alkali-soluble 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 is observed). It is preferably used with a polymer having a structural unit represented by.

The content of the acrylic binder resin or cardo-based binder resin in the alkali-soluble resin may be the same as the content of the structural unit-containing copolymer represented by Chemical Formula 1. When the content of the acrylic binder resin or cardo-based binder resin is the same as the content of the structural unit-containing copolymer represented by Formula 1, excellent developability and sensitivity may be obtained.

The alkali-soluble resin may be included in an amount of 1% to 20% by weight, such as 5% to 15% by weight, such as 10% to 15% 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) Photopolymerization 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 (4).

[Formula 4]

In Chemical Formula 4,

R ¹⁸ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ³ 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 4 may include 2 to 6 functional groups represented by Formula 4. In this case, sufficient polymerization may occur during exposure in the pattern formation process, thereby forming 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 4 may be a compound represented by Formula 5 or Formula 6.

[Formula 5]

[Formula 6]

In Formulas 5 and 6,

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

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

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.

Examples of commercially available products of the monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond 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 the V-260 ^® , V-312 ^® , and V-335 HP ^{® from} Osaka Yuki Chemical High School. 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 5% to 15% by weight, such as 10% to 15% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, 　 is sufficiently cured during exposure in the pattern formation process, resulting in excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

(C) Light polymerization Initiator

The photopolymerization initiator in the photosensitive resin composition according to an embodiment 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-based 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, benzyl dimethyl ketal, and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'- Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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 compound include 1,2-octanedione, O-acyloxime compound, 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 and the like can be used. As a specific example of the O-acyloxime compound, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1- (4-phenylsulfanylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O -Benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-oneoxime-O-acetate and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime-O-acetate I can.

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, a biimidazole compound, or a fluorene compound.

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, photopolymerization occurs sufficiently during exposure in a pattern formation process for manufacturing a color filter, so that sensitivity is excellent and transmittance is improved.

(D) colorant

As a colorant in the photosensitive resin composition according to an embodiment, a black colorant is used to improve light-shielding properties, and may include, for example, an inorganic black pigment, an organic black pigment, or a combination thereof. In addition, black pigments through color mixtures such as RGB black may be used alone or in combination.

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, and a solvent. In this case, the solid content of the pigment may be included in 5% to 30% by weight, such as 8% to 15% by weight, such as 8% 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.

For example, the black colorant may include aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, or a combination thereof. The RGB black refers to a pigment that exhibits black by mixing at least two kinds of colored pigments (not black) such as a red pigment, a green pigment, a blue pigment, a violet pigment, a yellow pigment, and a purple pigment.

According to one embodiment, a mixture of two different black colorants may be used as the colorant. In this case, it is possible to further improve other characteristics, such as electrical characteristics, while having sufficient light blocking performance to be applied to an organic light-emitting device or the like.

For example, the colorant in the photosensitive resin composition according to an embodiment may be a mixture of two different black colorants in a weight ratio of 1:1. When two types of black colorants different from each other are mixed in the same weight, light-shielding property can be further improved.

The colorant may be included in an amount of 1% to 20% by weight, such as 2% to 15% by weight, based on the solid content based on the total amount of the photosensitive resin composition. For example, the colorant may be included in an amount of 10% to 30% by weight, such as 15% to 25% by weight, based on the total amount of the photosensitive resin composition. When the black colorant is included within the above range, the coloring effect and development performance are excellent.

(E) solvent

The solvent in the photosensitive resin composition according to an embodiment may be materials that have compatibility with the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant (or a dispersion containing the same) 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 methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxy propionate 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-alkoxypropionate 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 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, 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 and propylene glycol propyl ether acetate can be used.

The solvent may be included in a balance, such as 30% to 70% by weight, such as 30% to 60% 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 photosensitive resin film.

(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 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 occurring, 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 544 ^® , F 554 ^®, etc. of Dai-Nippon Inki Chemical 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, What is marketed under a name 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 wettability to an IZO substrate or a glass substrate is 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 negative type. When the photosensitive resin composition is of a negative type, after exposure and development of the composition having a light-shielding property, residues in a region to which the pattern is exposed may be more completely removed.

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

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

(1) Application and film formation step

After applying the photosensitive resin composition to a desired thickness on a substrate such as a glass substrate or an ITO substrate subjected to a predetermined pretreatment using a method such as 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 the mask is interposed to form a pattern required for 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, so that only the exposed portions remain to form a pattern.

(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 of 250° C. or higher for 1 hour.

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

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

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

(Example)

(Polysiloxane resin synthesis)

Synthesis example 1 to Synthesis example 5 and Comparative Synthesis Example One

1 kg of a mixed solvent in which water and toluene are mixed at a weight ratio (wt%) of 5:5 was added to a three-necked flask, and then, while maintaining and stirring at 65°C, each of the monomers listed in Table 1 was added to the mol% shown in Table 1 below. 300 g of the mixture mixed according to the ratio was added dropwise over 2 hours. After the dropping was completed, a condensation polymerization reaction was performed while heating at 70° C. for 5 hours, and after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in toluene. The obtained siloxane solution was washed with water to remove the organic acid used as a catalyst, and additionally, the neutral polymer solution was distilled under reduced pressure to remove toluene to obtain polysiloxane resins of Synthesis Examples 1 to 5 and Comparative Synthesis Example 1. As a result of measuring the molecular weight of the synthesized polysiloxane resin through gel permeation chromatography (GPC), the molecular weight converted to a polystyrene standard sample was 1,300 g/mol. For example, the polysiloxane resins of Synthesis Examples 1 to 3 may be represented by the general formula of Formula E-1 below.

Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Comparative Synthesis Example 1 Phenyltrimethoxysilane 50 30 20 60 - 60 Methacrylpropyl trimethoxysilane 20 20 20 20 60 - Phenylmethyldimethoxysilane 10 30 40 - 20 20 1,3-Bis(3-aminopropyl)tetramethyldisiloxane 20 20 20 20 20 20 Molecular weight (g/mol) 1,300 1,400 1,600 1,500 1,400 1,500

[Formula E-1]

(Manufacture of alkali-soluble resin)

Manufacturing example One

While passing nitrogen through a 4-neck flask equipped with a stirrer, temperature controller, nitrogen gas injection device, and cooler, 30 g of DMAc was added, and 4,4'-hexafluoroisopropylidene) diphthalic anhydride ( 6-FDA) 12.3g was added and dissolved. When the solid was completely dissolved, 3.25 g of diamine benzoic acid (DAB) was added and stirred at room temperature for 2 hours. Then, 3.5 g of the polysiloxane resin of Synthesis Example 1 was added and stirred at room temperature for 1 hour. After the temperature was raised to 90° C., 5.6 g of pyridine and 2.05 g of acetic anhydride (A2CO) were added and stirred for 3 hours. After cooling the temperature in the reactor to room temperature, 1.6 g of 2-hydroethyl methacrylate (HEMA) was added and reacted for 6 hours to terminate the reaction. The reaction mixture was added to water to generate a precipitate, and 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 polyimide-polysiloxane copolymer. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 7,500 g/mol.

Manufacturing example 2

A polyimide-polysiloxane copolymer was prepared in the same manner as in Preparation Example 1, except that the polysiloxane resin of Synthesis Example 2 was used instead of the polysiloxane resin of Synthesis Example 1. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 8,300 g/mol.

Manufacturing example 3

A polyimide-polysiloxane copolymer was prepared in the same manner as in Preparation Example 1, except that the polysiloxane resin of Synthesis Example 3 was used instead of the polysiloxane resin of Synthesis Example 1. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 8,500 g/mol.

Manufacturing example 4

A polyimide-polysiloxane copolymer was prepared in the same manner as in Preparation Example 1, except that the polysiloxane resin of Synthesis Example 4 was used instead of the polysiloxane resin of Synthesis Example 1. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 8,700 g/mol.

Manufacturing example 5

A polyimide-polysiloxane copolymer was prepared in the same manner as in Preparation Example 1, except that the polysiloxane resin of Synthesis Example 5 was used instead of the polysiloxane resin of Synthesis Example 1. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 8,500 g/mol.

Comparative Production Example One

A polyimide-polysiloxane copolymer was prepared in the same manner as in Preparation Example 1, except that the polysiloxane resin of Comparative Synthesis Example 1 was used instead of the polysiloxane resin of Synthesis Example 1. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 8,700 g/mol.

Comparative Production Example 2

While passing nitrogen through a 4-neck flask equipped with a stirrer, temperature controller, nitrogen gas injection device, and cooler, 30 g of DMAc was added, and 4,4'-hexafluoroisopropylidene) diphthalic anhydride ( 6-FDA) 12.3g was added and dissolved. When the solid was completely dissolved, 3.25 g of diamine benzoic acid (DAB) was added and stirred at room temperature for 2 hours. Then, 3.5 g of aminopropyltetramethyldisiloxane was added and stirred at room temperature for 1 hour. After the temperature was raised to 90° C., 5.6 g of pyridine and 2.05 g of acetic anhydride (A2CO) were added and stirred for 3 hours. After cooling the temperature in the reactor to room temperature, 1.6 g of 2-hydroethyl methacrylate (HEMA) was added and reacted for 6 hours to terminate the reaction. The reaction mixture was added to water to generate a precipitate, and 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 polyimide-polysiloxane copolymer. The weight average molecular weight of the copolymer calculated by GPC (Gel Permeation Chromatography) method in terms of standard polystyrene was 6,700 g/mol.

(Production of photosensitive resin composition)

Example One

After dissolving 12 g of the alkali-soluble resin of Preparation Example 1 in 43 g of a solvent (PGMEA), 8 g of a polyfunctional monomer (DPHA; Japan Catalyst), a black colorant dispersion (BK-6616 (Tokushiki, 15% by weight solid content) 10g + TCD-006H (New Nippon Steel Co., Ltd., solid content 15% by weight) 10 g), photopolymerization initiator (OXE01; BASF Co., Ltd.) 2 g, surfactant (F-544; DIC Co., Ltd.) 0.5 g as an additive was added and sufficiently dissolved. Thereafter, it was filtered through a 0.45 µm fluorine resin filter to obtain a black photosensitive resin composition.

Example 2

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Preparation Example 2 was used instead of the alkali-soluble resin of Preparation Example 1.

Example 3

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Preparation Example 3 was used instead of the alkali-soluble resin of Preparation Example 1.

Example 4

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Preparation Example 4 was used instead of the alkali-soluble resin of Preparation Example 1.

Example 5

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Preparation Example 5 was used instead of the alkali-soluble resin of Preparation Example 1.

Comparative example One

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Comparative Production Example 1 was used instead of the alkali-soluble resin of Preparation Example 1.

Comparative example 2

A black photosensitive resin composition was obtained in the same manner as in Example 1, except that the alkali-soluble resin of Comparative Preparation Example 2 was used instead of the alkali-soluble resin of Preparation Example 1.

(evaluation)

Photosensitive Resin film Pattern formation

A cured film pattern was formed in the following manner using the black photosensitive resin composition according to Examples 1 to 5, Comparative Example 1 and Comparative Example 2. A resin coating layer was formed by coating each black photosensitive resin composition at 300 rpm using K-SPINNER, a spin coater of SEMES, on a glass substrate having a clean surface. After coating, it was dried on a hot plate at 100° C. for 100 seconds so that the thickness of the coated film was 1.5 μm. Subsequently, an active ray energy ray such as ultraviolet rays was exposed through a mask (gap of 100 μm) in a range of 100 mJ/cm2 of irradiation energy dose. The film obtained by exposure was developed (developing time 120 seconds) using a developer (2.38% TMAH aqueous solution, 23° C.) to form a cured film pattern. After development, it was placed in a convection oven at 350° C. and post-baked for 1 hour.

Assessment 1: Scum and Residue

After coating the black photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 and 2, prebaking, exposure, and development processes were performed. During exposure, it was exposed with an i-line exposure machine (UX-1200SM, UHSIO) and developed in a 2.38% TMAH developer, thereby implementing a 20㎛ hole pattern. Then, after curing in a convection oven at 250° C. for 1 hour, the presence of Scum and residue was confirmed with Hitachi's S-4300 FE-SEM equipment, and the results are shown in Table 2 below.

Evaluation 2: developing margin

After coating the black photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 and 2, prebaking, exposure, and development processes were performed. During exposure, exposure with an i-line exposure machine (UX-1200SM, UHSIO) and development on a 2.38% TMAH developer, the development margin for ±10 seconds was confirmed based on the development time for implementing a 20㎛ hole pattern. Margin evaluation was performed through CD measurement with an optical microscope (MX51, Olympus), and the results are shown in Table 2 below.

Evaluation 3: Taper angle

After coating the black photosensitive resin composition according to Examples 1 to 5 and Comparative Examples 1 and 2, prebaking and exposure processes were performed. During exposure, an isolated line pattern of 15 μm was realized by exposure with an i-line exposure machine (i10c). Then, after curing in a convection oven at 250° C. for 1 hour, measurements were made with Hitachi's S-4300 FE-SEM equipment, and the results are shown in Table 2 below.

Presence of Scum and residue Development margin (㎛) Taper angle (°) -10 seconds +10 seconds Example 1 Nothing 19.8 20.3 37.5 Example 2 Nothing 19.7 20.3 31.2 Example 3 Nothing 19.5 20.4 21.1 Example 4 Nothing 19.5 20.6 >45 Example 5 Nothing 19.6 20.5 15.0 Comparative Example 1 多 18.1 20.9 >45 Comparative Example 2 少 18.9 20.9 18.1

As shown in Table 2, the photosensitive resin composition according to an embodiment uses a polymer containing a structural unit represented by Formula 1, which has a T-type and D-type siloxane structure as an alkali-soluble resin, thereby generating Scum and residues. It can be seen that there is little and the development margin is also excellent.

In addition, it can be seen that the polymer according to the present invention can control the taper characteristics while maintaining a similar dissolution rate according to the molar ratio. That is, by adjusting the taper characteristics according to the requirements of the applicable application, it is possible to ultimately improve the optical characteristics of applications such as organic light emitting devices.

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 not limiting.

Claims (11)

(A) an alkali-soluble resin containing a polymer having a structural unit represented by the following formula (1);
(B) colorants;
(C) photopolymerizable monomer;
(D) photoinitiator; And
(E) solvent
Photosensitive resin composition comprising:
[Formula 1]

In Formula 1,
X is a substituted or unsubstituted C1 to C20 alicyclic organic group or a substituted or unsubstituted C6 to C20 aromatic organic group,
Y is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, or a substituted or unsubstituted C6 to C20 arylene group,
Z is a linking group derived from Formula 2 below,
m and n are molar content, m is 30 to 80 mol%, n is 20 mol% to 70 mol%,
[Formula 2]
(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d
In Chemical Formula 2,
R ¹ to R ⁶ are each independently a hydrogen atom, an amine group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted A substituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, *-(C=O)R ⁷ (Where R ⁷ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C6 to C20 aryl group), (meth)acrylate group, (meth)acrylic A royloxy group or a combination thereof,
However, at least one of the R ¹ to R ⁶ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a C1 to C20 alkyl group substituted with a (meth) acrylate group or a (meth) acryloyloxy group at the terminal ego,
0<a<1, 0≤b<1, 0≤c<1, 0≤d<1, and a+b+c+d=1.
The method of claim 1,
Z is a photosensitive resin composition represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R ⁸ to R ¹⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryl group,
However, at least one of the R ⁸ to R ¹⁷ must be a (meth) acrylate group, a (meth) acryloyloxy group, or a (meth) acrylate group or a (meth) acryloyloxy group substituted at the terminal C1 to C20 It is an alkyl group.
The method of claim 2,
The R ⁸ , R ⁹ and R ¹⁵ to R ¹⁷ are each independently a substituted or unsubstituted C1 to C20 alkyl group,
R ¹⁰ and R ¹⁴ are each independently a substituted or unsubstituted C6 to C20 aryl group,
R ¹¹ and R ¹³ are each independently a substituted or unsubstituted C1 to C20 alkoxy group,
The R ¹² is a (meth) acrylate group, a (meth) acryloyloxy group, or a (meth) acrylate group or a (meth) acryloyloxy group at the terminal is substituted C1 to C20 alkyl group of a photosensitive resin composition.
The method of claim 1,
The m and n is a photosensitive resin composition having a molar ratio of 1.2: 1 to 2: 1.
The method of claim 1,
The polymer is a photosensitive resin composition having a weight average molecular weight of 1,000 g / mol to 20,000 g / mol.
The method of claim 1,
The colorant photosensitive resin composition comprising an inorganic black pigment, an organic black pigment, or a combination thereof.
The method of claim 1,
The photosensitive resin composition, relative to the total amount of the photosensitive resin composition
1% to 20% by weight of the alkali-soluble resin;
5% to 15% by weight of the photopolymerizable monomer;
0.1% to 5% by weight of the photopolymerization initiator;
1% to 20% by weight of the colorant; And
Solvent balance
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
A photosensitive resin film produced using the photosensitive resin composition of any one of claims 1 to 8.
A display device comprising the photosensitive resin film of claim 9.
The method of claim 10,
The display device is an organic light emitting device (OLED).