KR102229633B1 - Photosensitive resin composition, photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) binder resin; (B) colorants; (C) a polymerizable monomer containing a (meth)acrylate compound, an oxetane compound, and a thiol group-containing compound; (D) photoinitiator; (E) a sulfonium-based cationic initiator; And (F) a photosensitive resin composition including a solvent, a photosensitive resin film prepared using the same, and a color filter including the photosensitive resin film.

Description

Photosensitive resin composition, photosensitive resin film and color filter using the same {PHOTOSENSITIVE RESIN LAYER USING THE SAME AND COLOR FILTER}

The present description relates to a photosensitive resin composition, a photosensitive resin film prepared by using the photosensitive resin composition, and a color filter including the photosensitive resin film.

A liquid crystal display device includes a lower substrate on which a light blocking layer, a color filter, and an ITO pixel electrode are formed; An active circuit unit composed of a liquid crystal layer, a thin film transistor, and a capacitor layer; And an upper substrate on which an ITO pixel electrode is formed.

The color filter is manufactured through a series of processes, such as application of a photosensitive resin composition, pre-baking, exposure, development, and post-baking processes, and the post-baking process is performed at a high temperature of 230°C or higher. In addition, there is a problem in that the color characteristics of the color filter are deteriorated by the post-baking process performed at the high temperature.

Accordingly, there is an increasing demand for a low-temperature curing photosensitive resin composition. Furthermore, in recent years, there is an increasing demand for a material suitable for an organic light-emitting device (OLED) process requiring low-temperature curing. In order to prevent reflection by external light, an organic light-emitting device (OLED) generally includes a polarizing film, which prevents reflection by external light, but reduces the luminous efficiency of the device and increases the manufacturing cost. Because there is.

In order to solve this problem, a method of improving the black visual sensation when the power is off by using an anti-reflection color filter instead of a polarizing film was devised. A liquid crystal display that can be manufactured even at a high temperature, for example, 200°C or higher. Unlike color filters applied to (LCD), color filters applied to organic light-emitting devices (OLEDs) have a limitation that must be manufactured in a low-temperature process.

That is, when a conventional photosensitive resin composition is cured at a low temperature, color change occurs and durability is deteriorated.Therefore, it has not yet been possible to provide a low-temperature curing type photosensitive resin composition that meets the above requirements, and the conventional photosensitive resin composition is used as an organic light emitting device (OLED). There is a limitation in application, and therefore, research on a low-temperature curing photosensitive resin composition that can be applied to an organic light-emitting device (OLED) is continuing.

One embodiment is to provide a photosensitive resin composition having excellent developability, film residual rate, and chemical resistance even after low-temperature curing.

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

Another embodiment is to provide a color filter including the photosensitive resin film.

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

One embodiment is (A) a binder resin; (B) colorants; (C) a polymerizable monomer containing a (meth)acrylate compound, an oxetane compound, and a thiol group-containing compound; (D) photoinitiator; (E) a sulfonium-based cationic initiator; And (F) It provides a photosensitive resin composition containing a solvent.

The oxetane-based compound may be represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group,

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

The thiol group-containing compound may be represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ³ is a substituted or unsubstituted C1 to C20 alkyl group,

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

The (meth)acrylate-based compound may be represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ⁵ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The sulfonium-based cationic initiator may be represented by the following formula (4).

[Formula 4]

(In Chemical Formula 4,

R ⁶ to R ⁹ are each independently a hydrogen atom, a halogen atom, 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 cyclic C2 to C20 heteroaryl group or a combination thereof,

m is an integer from 0 to 6,

n is an integer from 0 to 5.

The binder resin may include an acrylic binder resin, an epoxy binder resin, and a silsesquioxane compound having at least one reactive group in a molecular structure.

The acrylic binder resin may include structural units represented by the following Chemical Formulas 5-1 to 5-5.

[Chemical Formula 5-1]

[Chemical Formula 5-2]

[Chemical Formula 5-3]

[Chemical Formula 5-4]

[Chemical Formula 5-5]

In Formulas 5-1 to 5-5,

R ¹⁰ to R ¹⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to 10 alkoxy group,

L ⁹ is a substituted or unsubstituted C1 to C5 alkylene group,

p is an integer of 0 or 1.

The epoxy-based binder resin may include a structural unit represented by Formula 6 below.

[Formula 6]

The silsesquioxane compound may be represented by the following formula (7).

[Formula 7]

(R'SiO _3/2 ) _x (R'SiO _3/2 ) _y

In Chemical Formula 7,

R'and R'' are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or *-(L ^a ) _z -R''', At least one of R'and R'' is *-(L ^a ) _z -R''',

Wherein L ^a is a substituted or unsubstituted C1 to C20 alkylene group, *-L ^{b -OL c} -* or *-L ^d -C(=O)OL ^e -*, and L ^b To L ^e are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R''' is a hydrogen atom, a thiol group, an isocyanate group, a carboxyl group, a hydroxy group, an amino group, a urea group, a urethane group, a (meth)acrylate group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to A C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and ,

x is an integer from 1 to 500,

y is an integer from 1 to 500,

z is an integer of 0 or 1.

The silsesquioxane compound may be represented by Formula 8 below.

[Formula 8]

In Chemical Formula 8,

R ^a to R ^g are each independently selected from the group consisting of an unsubstituted C1 to C10 alkyl group and a substituent represented by the following formula 8-1,

[Chemical Formula 8-1]

In Formula 8-1,

L ¹⁰ and L ¹¹ are each independently a substituted or unsubstituted C1 to C10 alkylene group.

The photosensitive resin composition may further include a curing accelerator.

The curing accelerator may be an imidazole-based curing accelerator.

The imidazole-based curing accelerator may be represented by the following formula (9).

[Formula 9]

In Chemical Formula 9,

R ²⁰ to R ²³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

The curing accelerator may be any one selected from the group consisting of 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, and combinations thereof.

The photosensitive resin composition, based on the total weight of the photosensitive resin composition, the (A) binder resin 1% to 30% by weight; 20% to 50% by weight of the colorant (B); 1% to 20% by weight of the (C) polymerizable monomer; (D) 0.05% to 5% by weight of the photopolymerization initiator; 0.01% to 1% by weight of the (E) sulfonium-based cationic initiator; And 40% to 70% by weight of the (F) solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.

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

Another embodiment provides a color filter including the photosensitive resin film.

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.

As a photosensitive resin composition having excellent pattern resolution after development, a film residual film ratio after curing, and chemical resistance is provided, it can be usefully applied to a color filter or the like.

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 　, and , "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 , An azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a 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, It means substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

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

In the present specification, the cardo-based resin refers to a resin in which one or more functional groups selected from the group consisting of the following Chemical Formulas 10-1 to 10-11 are included in the backbone of the resin.

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) a binder resin; (B) colorants; (C) a polymerizable monomer containing a (meth)acrylate compound, an oxetane compound, and a thiol group-containing compound; (D) photoinitiator; (E) a sulfonium-based cationic initiator; And (F) a solvent.

Color filters using a photosensitive resin composition can be manufactured by coating three or more colors on a transparent substrate mainly by dyeing, electrodeposition, printing, and pigment dispersion. Recently, pigment dispersion technology has been improved to provide excellent color reproducibility. Pigment dispersion methods that ensure durability against heat, light, and humidity are mainly used. The color filter using such a pigment dispersion method realizes high luminance and high contrast ratio by using pigment micronization and surface treatment, or recently, development of a high-performance color filter to which a dye is applied is in progress. In addition, the types of substrates are being diversified to make the display flexible, and in particular, it is necessary to develop a color filter that will satisfy limited process conditions for the production of color filters in organic plastic substrates.

In particular, in the case of a display using a plastic substrate, a low-temperature process is required because thermal deformation occurs during a high-temperature process, and the demand for a low-temperature curable resin composition is increasing because only a low-temperature process is possible for the organic light emitting device (OLED) material. . However, due to insufficient curing during low temperature curing, there is a problem in that heat resistance and chemical resistance are weak. One embodiment relates to a photosensitive resin composition for a color filter having excellent heat resistance and chemical resistance due to a high degree of curing at a low temperature.

The photosensitive resin composition according to an embodiment uses a mixture of three different compounds ((meth)acrylate-based compounds, oxetane-based compounds, and thiol group-containing compounds) as polymerizable monomers, and includes a sulfonium-based cationic initiator together Thus, excellent resolution and durability can be secured even in a low-temperature curing process.

Furthermore, the photosensitive resin composition according to an embodiment may further include a curing accelerator, wherein the curing accelerator promotes a thermosetting reaction of the photosensitive resin composition, thereby preventing pattern infringement that may occur during the development process, thereby realizing a high-resolution fine pattern. This is possible. In addition, flow of the pattern that may occur in the post-baking process is prevented, so that the taper angle can be maintained relatively high, and the cohesive force inside the pattern is improved, so that the adhesion of the pattern can be increased.

Hereinafter, each component will be described in detail.

(C) Polymerizable Monomer

The polymerizable monomer is, for example, an oxetane-based compound (thermopolymerizable monomer) represented by the following formula (1), a thiol group-containing compound (photo/thermopolymerizable monomer) represented by the following formula (2), and (meth)acrylic represented by the following formula (3). It may contain a rate-based compound (photopolymerizable monomer).

[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,

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

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

R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ⁵ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group.

The polymerizable monomer may include an oxetanyl group, a thiol group, and a (meth)acrylate group to increase the degree of curing during photocuring and thermal curing.

Specifically, the reactivity of the sulfonium-based cationic initiator can be greatly improved by using an oxetane-based compound that is a thermally polymerizable monomer, and by additionally using a thiol group-containing compound that can play both the role of a photopolymerizable monomer and a thermally polymerizable monomer The crosslinking efficiency can be further increased. Furthermore, by using a sulfonium-based compound instead of a peroxide-based compound commonly used as a cationic initiator, the reactivity of the oxetanyl group can be greatly increased.

In addition, since the thiol group-containing compound represented by Chemical Formula 2 is located in the middle of the compound rather than at the end of the compound, the odor problem generated during the color filter process can be solved.

In addition, the (meth)acrylate-based compound represented by Formula 3 used as a photopolymerizable monomer has an ethylenically unsaturated double bond, so that sufficient polymerization occurs during exposure in the pattern formation process, resulting in excellent heat resistance, light resistance, and chemical resistance. Can be formed.

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

The polymerizable monomer may be included in an amount of 1% to 20% by weight, such as 1% to 10% by weight, based on the total amount of the photosensitive resin composition. When the polymerizable monomer is included within the above range, 　 curing occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, and excellent heat resistance, light resistance, chemical resistance, resolution and adhesion of the pattern.

(E) Sulfonium-based Cation Initiator

The photosensitive resin composition according to an embodiment includes a sulfonium-based cationic initiator, and the sulfonium-based cationic initiator may be included in a range of 0.01% to 1% by weight based on 100% by weight of the photosensitive resin composition.

In particular, when the sulfonium-based cationic initiator is included in an amount of more than 1% by weight, not only the straightness deteriorates due to excessive deterioration of melting characteristics during the post-baking process, but also the surface characteristics deteriorate.

The sulfonium-based cationic initiator may be used having an endothermic peak at a temperature of a post-baking process, such as a temperature of less than 200°C, such as 100°C to 170°C, as measured by differential scanning calorimetry. In the case of a sulfonium-based cationic initiator having an endothermic peak of 200° C. or higher by differential scanning calorimetry, the sulfonium-based cationic initiator is thermally decomposed at 200° C. or higher, which is a temperature similar to or higher than the thermosetting temperature of the photosensitive resin composition. In addition, the sulfonium-based cationic initiator cannot serve to polymerize the epoxy-based binder resin to be described later before thermal curing of the photosensitive resin composition, or the reaction rate becomes too slow. Accordingly, when the photosensitive resin composition is cured, the epoxy-based binder resin is polymerized so that it cannot play a role of holding the photosensitive resin film, and the above object cannot be achieved.

The sulfonium-based cationic initiator may include, for example, a compound represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

R ⁶ to R ⁹ are each independently a hydrogen atom, a halogen atom, 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 cyclic C2 to C20 heteroaryl group or a combination thereof,

m is an integer from 0 to 6,

n is an integer from 0 to 5.

As described above, the sulfonium-based cationic initiator accelerates the polymerization reaction of the epoxy-based binder resin, so that a high-resolution fine pattern can be realized. For example, the polymerization reaction of the epoxy-based binder resin consists of a thermal decomposition (or photolysis) step, an initiation step, and a polymerization step of a sulfonium-based cationic initiator, and each step is shown in Reaction Schemes 1 to 3 below.

[Scheme 1]

[Scheme 2]

[Scheme 3]

In Reaction Schemes 1 to 3, R ⁶ to R ⁹ , R ^x and R ^y are each independently a hydrogen atom, a halogen atom, 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, a substituted or unsubstituted C2 to C20 heteroaryl group, or a combination thereof, w is the number of moles of the epoxy-based binder resin participating in the reaction, and m is an integer of 0 to 6. .

Examples of the epoxy-based binder resin include a phenol novolac epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an alicyclic epoxy resin, or a combination thereof, but is limited thereto. It is not. The epoxy-based binder resin will be described later.

(A) binder resin

The binder resin may include an acrylic binder resin, an epoxy binder resin, and a silsesquioxane compound having at least one reactive group in a molecular structure.

The acrylic binder resin may include structural units represented by the following Chemical Formulas 5-1 to 5-5.

[Chemical Formula 5-1]

[Chemical Formula 5-2]

[Chemical Formula 5-3]

[Chemical Formula 5-4]

[Chemical Formula 5-5]

In Formulas 5-1 to 5-5,

R ¹⁰ to R ¹⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to 10 alkoxy group,

L ⁹ is a substituted or unsubstituted C1 to C5 alkylene group,

p is an integer of 0 or 1.

The acrylic binder resin includes the structural units represented by Chemical Formulas 5-1 to 5-5, and can secure high heat resistance and high luminance characteristics while controlling the developability of the pattern, and furthermore, the binder resin is a cardo-based resin to be described later. When a binder resin is further included, a fine pattern can be realized by increasing the adhesion of the pattern, and a high resolution can be obtained and a high transmittance can be secured.

The epoxy-based binder resin may include a structural unit represented by Formula 6 below.

[Formula 6]

The silsesquioxane compound may be represented by the following formula (7).

[Formula 7]

(R'SiO _3/2 ) _x (R'SiO _3/2 ) _y

In Chemical Formula 7,

R'and R'' are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or *-(L ^a ) _z -R''', At least one of R'and R'' is *-(L ^a ) _z -R''',

Wherein L ^a is a substituted or unsubstituted C1 to C20 alkylene group, *-L ^{b -OL c} -* or *-L ^d -C(=O)OL ^e -*, and L ^b To L ^e are each independently a substituted or unsubstituted C1 to C20 alkylene group,

R''' is a hydrogen atom, a thiol group, an isocyanate group, a carboxyl group, a hydroxy group, an amino group, a urea group, a urethane group, a (meth)acrylate group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 heterocycloalkyl group (eg, epoxy group, etc.), substituted or unsubstituted C6 to C20 aryl group or substituted or unsubstituted C2 To C20 heteroaryl group,

x is an integer from 1 to 500,

y is an integer from 1 to 500,

z is an integer of 0 or 1.

For example, the silsesquioxane compound may be represented by the following formula (8).

[Formula 8]

In Chemical Formula 8,

R ^a to R ^g are each independently selected from the group consisting of an unsubstituted C1 to C10 alkyl group and a substituent represented by the following formula 8-1,

[Chemical Formula 8-1]

In Formula 8-1,

L ¹⁰ and L ¹¹ are each independently a substituted or unsubstituted C1 to C10 alkylene group.

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

The cardo-based binder resin may be represented by Formula 10 below.

[Formula 10]

In Chemical Formula 10,

R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom or a substituted or unsubstituted (meth)acryloyloxy alkyl group,

R ¹⁰³ and R ¹⁰⁴ 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 ¹⁰⁷ R ¹⁰⁸ , SiR ¹⁰⁹ R ¹¹⁰ (wherein R ¹⁰⁷ to R ¹¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) or the following It is any one of the linking groups represented by Chemical Formulas 10-1 to 10-11,

[Formula 10-1]

[Formula 10-2]

[Formula 10-3]

[Formula 10-4]

[Formula 10-5]

(In Chemical Formula 10-5,

R ^z 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 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid anhydride residue or an acid dianhydride residue,

z1 and z2 are each independently an integer of 0 to 4 ek.

The weight average molecular weight of the cardo-based binder resin may be 500 g/mol to 50,000 g/mol, such as 1,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, a pattern can be formed well without residue 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 11 below at at least one of both ends.

[Formula 11]

In Formula 11,

Z ³ may be represented by the following Chemical Formulas 11-1 to 11-7.

[Formula 11-1]

(In Formula 11-1, R ^h and R ⁱ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.)

[Formula 11-2]

[Formula 11-3]

[Formula 11-4]

[Formula 11-5]

(In Formula 11-5, R ^j is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 alkenylamine group.)

[Formula 11-6]

[Formula 11-7]

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

When the binder resin further includes a cardo-based binder resin, the photosensitive resin composition has excellent developability, and has good sensitivity during photocuring, and thus has excellent fine pattern formation.

The binder resin may be included in an amount of 1% to 30% by weight, such as 1% to 20% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

(B) 　Coloring agent

The colorant may include a pigment, a dye, or a combination thereof, and the pigment may include an organic pigment, an inorganic pigment, or a combination thereof.

For example, the pigment may further include the black pigment, red pigment, green pigment, blue pigment, yellow pigment, or a combination thereof.

Examples of the black pigment may include aniline black, perylene black, titanium black, cyanine black, carbon black, or a combination thereof, but are not limited thereto. Meanwhile, when the black pigment is used, it may be used together with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment, and an azo pigment.

Examples of the red pigment include 　C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89 etc. are mentioned. Examples of the green pigment include C.I. Green pigment 58, C.I. Green pigment 57, C.I. Green pigment 36, C.I. And halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like. Examples of the blue pigment include C.I. Blue pigment 15:6, C.I. Blue pigment 15, 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. Copper phthalocyanine pigments, such as blue pigment 16, are mentioned. Examples of the yellow pigment include C.I. Isoindolin-based pigments such as yellow pigment 139, C.I. Quinophthalone pigments such as yellow pigment 138, C.I. And nickel complex pigments such as yellow pigment 150 and the like. The pigments may be used alone or in combination of two or more, and are not limited to these examples.

A dispersant may be used together to disperse the pigment in the photosensitive resin composition. Specifically, the pigment may be previously surface-treated with a dispersant, or may be used by adding a dispersant together with the pigment when preparing the photosensitive resin composition. That is, the pigment may be included in the photosensitive resin composition in the form of a pigment dispersion. The pigment dispersion may include a pigment solid content, a dispersant, a solvent, and the like, and the pigment solid content may be included in an amount of 8% to 15% by weight, such as 8% to 12% by weight, based on the total amount of the pigment dispersion.

Nonionic dispersants, anionic dispersants, cationic dispersants, and the like may be used as the dispersant. Specific examples of the dispersant include polyalkylene glycol and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more.

Examples of commercially available products of the above dispersant are BYK's DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. from EFKA Chemical; Zeneka's Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; Alternatively, there are PB711 and PB821 of Ajinomoto.

The dispersant may be included in an amount of 0.1% to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the photosensitive resin composition has excellent dispersibility, and thus stability, developability, and patternability are excellent when the light-shielding layer is manufactured.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is pretreated and used, the average particle diameter of the pigment can be refined.

The pretreatment may be performed by kneading the pigment together with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

Kneading may be performed at a temperature of 40° C. to 100° C., and filtering and washing may be performed by washing the inorganic salt with water or the like, followed by filtration.

Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized, examples of which include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. Alkylene glycol monoalkyl ether; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and these may be used alone or in combination of two or more.

Pigments that have undergone the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively form a fine pattern while having excellent heat resistance and light resistance.

The colorant may be included in an amount of 20% to 50% by weight, such as 30% to 50% by weight, based on the total amount of the photosensitive resin composition. When the colorant is included within the above range, the color reproducibility is excellent, and the resolution and straightness of the pattern are excellent.

(D) Light polymerization Initiator

The photopolymerization initiator is an initiator generally used in the photosensitive resin composition, and for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, and the like can be used. .

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

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone compound include thioxanthone, 2-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 benzyldimethylketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4' -Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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, 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 and 1-(4-phenylsulfanylphenyl)-butan-1-oneoxime- O-acetate can be used.

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

The photopolymerization initiator may be 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-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, etc. Can be mentioned.

The photopolymerization initiator may be included in an amount of 0.05% to 5% by weight, such as 0.1% to 5% 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, chemical resistance, resolution and adhesion of the pattern, and decrease in transmittance due to unreacted initiator Can be prevented.

(F) solvent

The solvent has compatibility with the binder resin, the colorant, the polymerizable monomer, the photopolymerization initiator, the sulfonium-based cationic initiator, and a curing accelerator described below, but materials that do not react may be used.

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 and ethylene glycol monoethyl 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 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; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl methoxy acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-oxypropionic acid alkyl esters such as 3-oxy methyl propionate and 3-oxy ethyl propionate; 3-alkoxy propionic 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-oxy methyl propionate, 2-oxy ethyl propionate, and 2-oxy propionate propyl; 2-alkoxy propionic 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-methyl propionic acid esters such as 2-oxy-2-methyl methyl propionate and 2-oxy-2-methyl ethyl propionate, 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methyl propionate such as ethyl methyl propionate; Esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, and 2-hydroxy-3-methyl methyl butanoate; 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, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents such as ethyl, diethyl oxalate, diethyl maleate, γ-butyrolactone, 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 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 may be used.

The solvent may be included in the balance, for example, 40% 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 light-shielding layer.

(G) hardening accelerator

The photosensitive resin composition according to an embodiment may further include a curing accelerator.

The curing accelerator may accelerate a curing reaction, such as a thermosetting reaction, between the polymerizable monomer and the epoxy-based binder resin.

The curing accelerator may be included in an amount of 0.1% to 1% by weight based on the total amount of the photosensitive resin composition. When the curing accelerator is contained in an amount of less than 0.1% by weight based on the total amount of the photosensitive resin composition, the curing speed becomes slow, resulting in poor pattern resolution, and a high taper angle cannot be formed, and the curing accelerator is 1 wt% based on the total amount of the photosensitive resin composition. When the content exceeds %, the curing speed becomes faster than necessary, and not only the straightness deteriorates, but also the adhesion is lowered due to excessive deterioration of melting characteristics during the post-baking process.

The curing accelerator may be an imidazole-based curing accelerator, and the imidazole-based curing accelerator may be represented by Formula 2 below.

[Formula 9]

In Chemical Formula 9,

R ²⁰ to R ²³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.

For example, the curing accelerator may be any one selected from the group consisting of 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, and combinations thereof.

(H) other additives

The photosensitive resin composition according to one embodiment is malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; Or it may further include a combination of these.

For example, the photosensitive resin composition may further include a silane-based coupling agent having a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion to the substrate.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ-gly Cidoxy propyl trimethoxysilane, 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, 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; ^{Mecha Pack F 142D ®} , F 172 ^® , F 173 ^® , F 183 ^®, etc. of Dai Nippon Inki 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 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 the glass substrate 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.

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

Another embodiment provides a color filter and a display device (eg, an organic light emitting device, etc.) including the photosensitive resin film. The manufacturing method of the color filter is as follows.

(1) Application and film formation step

The above-described photosensitive resin composition is applied onto a substrate subjected to a predetermined pretreatment to a desired thickness, for example, a thickness of 1.2 µm to 3.5 µm by using a method such as spin or slit coating, roll coating, screen printing, and applicator method. After application, the coating film is formed by heating at a temperature of 70° C. to 90° C. for 1 to 10 minutes to remove the solvent.

(2) exposure step

In order to form a pattern required for the obtained coating film, a mask of a predetermined shape is interposed, and then 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 photosensitive resin composition, but, for example, 500 mJ/cm ^{2 when using a high-pressure mercury lamp.} It is below (by 365 nm sensor).

(3) development stage

Following 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 an image pattern.

(4) Post-processing step

In order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability, etc., the image pattern obtained by the above development may be cured by heating again or irradiating with actinic rays.

By using the above-described photosensitive resin composition, excellent heat resistance and chemical resistance can be obtained even at a low temperature process, and thus, a photosensitive resin film manufactured using the photosensitive resin composition can be applied to a display device such as 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 )

(Production of photosensitive resin composition)

Example One, Example 2, Comparative example 1 to Comparative example 3, Reference example 1 and Reference example 2

Photosensitive resin compositions according to Examples 1 and 2, Comparative Examples 1 to 3, Reference Examples 1 and 2 were prepared using the components mentioned below in the composition shown in Table 1 below.

Specifically, after dissolving a photopolymerization initiator, an epoxy binder resin, a curing accelerator and/or a thermosetting initiator in a solvent, the mixture was stirred at room temperature for about 2 hours. Subsequently, an acrylic binder resin, a silsesquioxane compound, a colorant (pigment dispersion), and a polymerizable monomer were added, followed by stirring at room temperature for 2 hours. After the additive was added thereto, the mixture was stirred at room temperature for 1 hour, and the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

(A) binder resin

(A-1) Polysilsesquioxane (Arakawa, SQ506)

(A-2) Acrylic binder resin (Samsung SDI, 1000S)

(A-3) Epoxy binder resin (Dicel, EHPE-3150)

(B) colorant

(B-1) C.I. pigment Green 58 pigment dispersion (SKC company)

(B-2) C.I. pigment Yellow 138 pigment dispersion (ENF company)

(C) Polymerizable Monomer

(C-1) Photopolymerizable monomer: dipentaerythritol hexaacrylate (Japan Pharmaceutical Co., Ltd., DPHA)

(C-2) Thermally polymerizable monomer: oxetane-based compound (Toagosei, OXT-221)

(C-3) Photo/thermal polymerizable monomer: Thiol group-containing compound (Showadenko, KarenzMT PE 1)

(D) Light polymerization Initiator

(D-1) OXE01 (BASF company)

(D-2) IRG369 (BASFf company)

(E) Sulfonium-based Cation Initiator

TA-100 (San-Apro company)

(F) solvent

Propylene glycol monomethyl ether (PGME)

(G) hardening accelerator

Imidazole-based hardening accelerator (2-methyl imidazole) (Shikoku, Curezol 2MZ)

(H) other additives

Leveling agent (DIC, F-554)

(Unit: wt%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reference Example 1 Reference Example 2 (A) binder resin (A-1) 1.835 1.822 1.834 1.822 1.822 - - (A-2) 1.484 1.473 1.484 1.473 1.473 1.484 4.571 (A-3) 0.179 0.178 0.179 0.178 0.178 1.463 0.179 (B) colorant (B-1) 34.942 34.942 34.942 34.942 34.942 34.942 34.942 (B-2) 10.366 10.366 10.366 10.366 10.366 10.366 10.366 (C) polymerizable monomer (C-1) 3.663 3.637 3.663 4.224 4.087 3.663 3.663 (C-2) 0.663 0.659 0.663 - 0.659 0.663 0.663 (C-3) 0.453 0.450 0.453 0.522 - 0.453 0.453 (D) photopolymerization initiator (D-1) 0.173 0.172 0.216 0.172 0.172 0.173 0.173 (D-2) 0.093 0.092 0.093 0.092 0.092 0.093 0.093 (E) Sulfonium-based cationic initiator 0.043 0.043 - 0.043 0.043 0.043 0.043 (F) solvent 46.006 45.566 46.007 45.566 45.566 45.567 44.754 (G) hardening accelerator - 0.500 - 0.500 0.500 0.500 - (I) other additives 0.100 0.100 0.100 0.100 0.100 0.100 0.100 Sum 100.0 100.0 100.0 100.0 100.0 100.000 100.0

Evaluation 1: Evaluation of pattern resolution after development

The photosensitive resin compositions according to Example 1, Example 2, Comparative Examples 1 to 3, Reference Example 1 and Reference Example 2 were each 3 μm thick using a spin coater (Mikasa, Opticoat MS-A150) on a glass substrate. After coating with, soft-baking at 80℃ for 120 seconds using a hot-plate, and exposure with a power of 60mJ using an exposure machine (Ushio, ghi broadband) I did. Subsequently, it was developed with a 0.2% by weight aqueous solution of potassium hydroxide (KOH) using a developing device (SVS, SSP-200). Thereafter, the minimum µm of the remaining pattern was checked through an optical microscope, and the results are shown in Table 2 below.

Pattern resolution (㎛) Example 1 10 Example 2 10 Comparative Example 1 10 Comparative Example 2 20 Comparative Example 3 20 Reference Example 1 30 Reference Example 2 30

Evaluation 2: Film remaining rate evaluation

The photosensitive resin compositions according to Example 1, Example 2, Comparative Examples 1 to 3, Reference Example 1 and Reference Example 2 were each 3 μm thick using a spin coater (Mikasa, Opticoat MS-A150) on a glass substrate. After coating with, soft-baking at 80℃ for 120 seconds using a hot-plate, and exposure with a power of 60mJ using an exposure machine (Ushio, ghi broadband) I did. Subsequently, it was developed with a 0.2% by weight aqueous solution of potassium hydroxide (KOH) using a developing device (SVS, SSP-200). Thereafter, hard-baking was performed at 100° C., 150° C., and 200° C. for 30 minutes in a convection oven, and further cured at 200° C. for 30 minutes. By measuring the height of the pattern after hard-baking and the height of the pattern after further curing for each of the coating, exposure, development, and temperature, the residual film ratio was calculated, and the results are shown in Table 3 below.

Film remaining rate Evaluation standard

◎: Reduction of residual film within 2%

○: Reduction of residual film within 3%

△: Reduction of residual film within 5%

Ⅹ: Reduce residual film by more than 5%

Hard-baking temperature (℃) 100 150 200 Example 1 ○ ○ ◎ Example 2 ◎ ◎ ◎ Comparative Example 1 X △ ○ Comparative Example 2 Ⅹ △ ○ Comparative Example 3 Ⅹ △ ○ Reference Example 1 Ⅹ △ △ Reference Example 2 Ⅹ △ △

Evaluation 3: Chemical resistance evaluation

The photosensitive resin compositions according to Example 1, Example 2, Comparative Examples 1 to 3, Reference Example 1 and Reference Example 2 were each 3 μm thick using a spin coater (Mikasa, Opticoat MS-A150) on a glass substrate. After coating with, soft-baking at 80℃ for 120 seconds using a hot-plate, and exposure with a power of 60mJ using an exposure machine (Ushio, ghi broadband) I did. Subsequently, it was developed with a 0.2% by weight aqueous solution of potassium hydroxide (KOH) using a developing device (SVS, SSP-200). Thereafter, hard-baking was performed at 100°C, 150°C, and 200°C for 20 minutes in a convection oven, thereby obtaining a patterned coating film.

The coating film was immersed in an NMP solvent at 80° C. for 2 minutes to evaluate chemical resistance, and the results are shown in Table 4 below.

The chemical resistance was evaluated by the color change (ΔEab*) of the coating film before and after immersion in the NMP solvent, and the color change (ΔEab*) was measured using a spectrophotometer (Otsuka Electronics, MCPD3000).

Criteria for evaluation of chemical resistance

◎: ΔEab* is within 2%

○: ΔEab* is within 3%

△: ΔEab* is within 5%

Ⅹ: ΔEab* exceeds 5%

Color change (ΔEab*) Hard-baking temperature (℃) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reference Example 1 Reference Example 2 100 ○ ◎ Ⅹ Ⅹ Ⅹ △ △ 150 ○ ◎ △ △ △ △ △ 200 ◎ ◎ ○ ○ ○ ◎ ○

As shown in Tables 2 to 4, the coating film formed of the photosensitive resin composition according to one embodiment has less color change after NMP solvent treatment even at a low temperature curing temperature than the coating film formed of the photosensitive resin composition of Comparative Examples 1 to 3 In addition, it can be seen that the resolution and film residual rate are excellent. In addition, it can be seen that even when the photosensitive resin composition according to an embodiment does not contain a silsesquioxane compound, the resolution, film residual rate, and chemical resistance are also significantly reduced.

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 are 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) a binder resin including an acrylic binder resin, an epoxy binder resin, and a silsesquioxane compound having at least one reactive group in the molecular structure;
(B) colorants;
(C) a polymerizable monomer containing a (meth)acrylate compound, an oxetane compound, and a thiol group-containing compound;
(D) photoinitiator;
(E) a sulfonium-based cationic initiator; And
(F) solvent
Photosensitive resin composition comprising a.
The method of claim 1,
The oxetane-based compound is a photosensitive resin composition represented by the following Formula 1:
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted C1 to C20 alkyl group,
L ¹ and L ² are each independently a substituted or unsubstituted C1 to C20 alkylene group.
The method of claim 1,
The thiol group-containing compound is a photosensitive resin composition represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
R ³ is a substituted or unsubstituted C1 to C20 alkyl group,
L ³ and L ⁴ are each independently a substituted or unsubstituted C1 to C20 alkylene group.
The method of claim 1,
The (meth)acrylate-based compound is a photosensitive resin composition represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ⁵ to L ⁸ are each independently a substituted or unsubstituted C1 to C20 alkylene group.
The method of claim 1,
The sulfonium-based cationic initiator is a photosensitive resin composition represented by the following Formula 4:
[Formula 4]

(In Chemical Formula 4,
R ⁶ to R ⁹ are each independently a hydrogen atom, a halogen atom, 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 cyclic C2 to C20 heteroaryl group or a combination thereof,
m is an integer from 0 to 6,
n is an integer from 0 to 5.
delete The method of claim 1,
The acrylic binder resin is a photosensitive resin composition comprising a structural unit represented by Formula 5-1 to Formula 5-5:
[Chemical Formula 5-1]

[Chemical Formula 5-2]

[Chemical Formula 5-3]

[Chemical Formula 5-4]

[Chemical Formula 5-5]

In Formulas 5-1 to 5-5,
R ¹⁰ to R ¹⁷ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ¹⁸ and R ¹⁹ are each independently a substituted or unsubstituted C1 to 10 alkoxy group,
L ⁹ is a substituted or unsubstituted C1 to C5 alkylene group,
p is an integer of 0 or 1.
The method of claim 1,
The epoxy-based binder resin is a photosensitive resin composition comprising a structural unit represented by the following formula (6).
[Formula 6]

The method of claim 1,
The silsesquioxane compound is a photosensitive resin composition represented by the following formula (7):
[Formula 7]
(R'SiO _3/2 ) _x (R'SiO _3/2 ) _y
In Chemical Formula 7,
R'and R'' are each independently a hydrogen atom, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, or *-(L ^a ) _z -R''', At least one of R'and R'' is *-(L ^a ) _z -R''',
Wherein L ^a is a substituted or unsubstituted C1 to C20 alkylene group, *-L ^{b -OL c} -* or *-L ^d -C(=O)OL ^e -*, and L ^b To L ^e are each independently a substituted or unsubstituted C1 to C20 alkylene group,
R''' is a hydrogen atom, a thiol group, an isocyanate group, a carboxyl group, a hydroxy group, an amino group, a urea group, a urethane group, a (meth)acrylate group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to A C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and ,
x is an integer from 1 to 500,
y is an integer from 1 to 500,
z is an integer of 0 or 1.
The method of claim 9,
The silsesquioxane compound is a photosensitive resin composition represented by Formula 8 below:
[Formula 8]

In Chemical Formula 8,
R ^a to R ^g are each independently selected from the group consisting of an unsubstituted C1 to C10 alkyl group and a substituent represented by the following formula 8-1,
[Chemical Formula 8-1]

In Formula 8-1,
L ¹⁰ and L ¹¹ are each independently a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 1,
The photosensitive resin composition further comprises a curing accelerator.
The method of claim 11,
The curing accelerator is an imidazole-based curing accelerator photosensitive resin composition.
The method of claim 12,
The imidazole-based curing accelerator is a photosensitive resin composition represented by the following Formula 9:
[Formula 9]

In Chemical Formula 9,
R ²⁰ to R ²³ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a combination thereof.
The method of claim 11,
The curing accelerator is any one selected from the group consisting of 2-methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, and combinations thereof. Photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition, based on the total weight of the photosensitive resin composition,
(A) 1% to 30% by weight of the binder resin;
20% to 50% by weight of the colorant (B);
1% to 20% by weight of the (C) polymerizable monomer;
(D) 0.05% to 5% by weight of the photopolymerization initiator;
0.01% to 1% by weight of the (E) sulfonium-based cationic initiator; And
40% to 70% by weight of the solvent (F)
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent containing a vinyl group or a (meth)acryloxy group; Leveling agents; Fluorine-based surfactant; Or a photosensitive resin composition further comprising a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 5 and 7 to 16.
A color filter comprising the photosensitive resin film of claim 17.
A display device comprising the photosensitive resin film of claim 17.
The method of claim 19,
The display device is an organic light emitting device (OLED).