TW202208987A - Photosensitive resin composition and photosensitive resin layer using the same and color filter - Google Patents

Abstract

Disclosed are a photosensitive resin composition, a photosensitive resin layer manufactured using the same, and a color filter including the photosensitive resin layer. The photosensitive resin composition includes (A) a binder resin including an acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant including a phthalocyanine-based dye; and (E) a solvent, wherein the acryl-based binder resin includes a structural unit represented by Chemical Formula 2, the acryl-based binder resin further includes at least one selected from structural units represented by Chemical Formula 1 and Chemical Formula 3, and the acryl-based binder resin includes 5 wt% to 25 wt% of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based binder resin.

Description

Photosensitive resin composition, photosensitive resin layer and color filter using the same

The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter including the photosensitive resin layer. CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0108055 filed in the Korean Intellectual Property Office on Aug. 26, 2020, the entire contents of which are incorporated herein by reference.

Among many types of displays, liquid crystal display devices have advantages in brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have become more widely used in laptop computers, monitors, and TVs Screen. A liquid crystal display device includes: a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed; and an upper substrate on which an active circuit portion and ITO pixel electrodes are formed, the active circuit Parts include a liquid crystal layer, a thin film transistor, and a capacitor layer.

Each pixel is formed by sequentially stacking a plurality of color filters (generally, formed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)) in a predetermined order. Whereas, color filters are formed in pixel regions, and a black matrix layer is placed in a predetermined pattern on a transparent substrate to form boundaries between pixels.

The pigment dispersion method, which is one of the methods of forming a color filter, provides a color film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix on, exposing the formed pattern to light, removing the unexposed portion with a solvent, and thermally curing it.

Colored photosensitive resin compositions used for producing color filters according to the pigment dispersion method generally contain a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a colorant, a solvent, and other additives. Pigment dispersion methods having such properties are actively used in the manufacture of LCDs for mobile phones, laptop computers, monitors, and TVs.

However, in recent years, even in photosensitive resin compositions for color filters using pigment dispersion methods that have various advantages, there are still various problems, such as the need for a powder refining process, the use of additives for stable dispersion Demand and storage and transportation of pigment dispersions are difficult. That is, despite the excellent processability of pigments, there is still a limit to finely dispersing pigment particles that affect brightness improvement. In recent years, it has also acted as a cause of ACC failure, which is a problem with LCD displays.

Accordingly, there has arisen a need to develop dyes, rather than pigments, that do not require separate refining and dispersion processes.

Compared with pigments, dyes in a single molecule state can have high solubility, high brightness, and high contrast ratio. Since dyes have weaker heat resistance and durability than pigments, they may be susceptible to processing solvents used in the LCD panel manufacturing process. Therefore, there is a limit to completely replacing the pigment with the dye, and in order to solve this situation, methods such as limiting the amount of the dye or coating an epoxy-based binder resin having good chemical resistance have been used. However, if the amount of the dye in the composition is high, the developability may be deteriorated, and thus non-development may occur or residues may be generated on the organic layer after development.

The embodiment provides a photosensitive resin composition that achieves high brightness and excellent chemical resistance, improves residue characteristics on an organic layer after development, and does not cause pattern tearing.

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

Another embodiment provides a color filter including a photosensitive resin layer.

[化學式2]

[化學式3]

The embodiment provides a photosensitive resin composition comprising: (A) a binder resin containing acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator (D) a coloring agent containing a phthalocyanine dye; and (E) a solvent, wherein the acryl-based binder resin comprises a structural unit represented by Chemical Formula 2, and the acryl-based binder resin further comprises a compound selected from the group consisting of Chemical Formula 1 and Chemical Formula 3 At least one of the represented structural units, and the acryl-based adhesive resin contains 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based adhesive resin. [Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

In Chemical Formula 1 to Chemical Formula 3, R ⁰ and R ¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R ² is a substituted or unsubstituted C3 to C20 cycloalkyl group or A fused ring of two or more C3 to C20 cycloalkane rings, and L ¹ is a substituted or unsubstituted C1 to C20 alkylene.

The phthalocyanine-based dye may be contained in an amount of 30% by weight or more based on the total amount of the photosensitive resin composition.

[化學式1-2]

[化學式1-3]

The structural unit represented by Chemical Formula 1 may be at least one selected from the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3. [Chemical formula 1-1]

[Chemical formula 1-2]

[Chemical formula 1-3]

[化學式3-2]

The structural unit represented by Chemical Formula 3 may be a structural unit represented by Chemical Formula 3-1 or Chemical Formula 3-2. [Chemical formula 3-1]

[Chemical formula 3-2]

In Chemical Formula 3-1 and Chemical Formula 3-2, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group.

The acryl-based binder resin may further include a structural unit represented by Chemical Formula 4. [Chemical formula 4]

In Chemical Formula 4, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L ² is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

The acryl-based binder resin may further include a structural unit represented by Chemical Formula 5. [Chemical formula 5]

In Chemical Formula 5, R ³ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, or a substituted or unsubstituted C2-C20 heterocyclic group substituted or unsubstituted C6 to C20 aryl, and n is an integer from 0 to 5.

The acryl-based binder resin may include a structural unit represented by Chemical Formula 1-2, a structural unit represented by Chemical Formula 1-3, a structural unit represented by Chemical Formula 2, and a structural unit represented by Chemical Formula 4, and to constitute acryl-based The structural unit represented by Chemical Formula 2 may be contained in an amount smaller than the amount of the structural unit represented by Chemical Formula 4 in terms of the total amount of solids of the binder resin.

The acryl-based adhesive resin may contain 1 to 10 wt % of the structural unit represented by Chemical Formula 1-2, 20 to 50 wt % of the The structural unit represented by Chemical Formula 1-3, 15 wt % to 25 wt % of the structural unit represented by Chemical Formula 2, and 30 wt % to 50 wt % of the structural unit represented by Chemical Formula 4.

The acryl-based binder resin may contain 15 to 25 wt % of the structural unit represented by Chemical Formula 1-1, 5 to 15 wt % of the The structural unit represented by Chemical Formula 2, 25 to 35 wt % of the structural unit represented by Chemical Formula 3-1, 15 to 30 wt % of the structural unit represented by Chemical Formula 3-2, and 15 to 25 wt % The structural unit represented by Chemical Formula 5.

The acryl-based binder resin may have a weight average molecular weight of 10,000 g/mol to 20,000 g/mol.

The phthalocyanine-based dye may be represented by Chemical Formula 6. [Chemical formula 6]

其中，在化學式7中， R²⁰ 和R²¹ 各自獨立地為經C1到C5烷基取代或未經C1到C5烷基取代的C1到C10烷基，以及 o和p各自獨立地為0到5的整數，前提為1 ≤ o p ≤ 5。In Chemical Formula 6, R ⁴ to R ¹¹ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, R ¹² to R ¹⁹ are each independently a hydrogen atom, and at least one of R ⁴ to R ⁷ and at least one of R ⁸ to R ¹¹ are each independently represented by Chemical Formula 7, [Chemical Formula 7]

wherein, in Chemical Formula 7, R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl substituted or unsubstituted with a C1 to C5 alkyl group, and o and p are each independently 0 to 5 An integer of , provided that 1 ≤ op ≤ 5.

In Chemical Formula 6, R ⁶ and R ⁹ may each independently be represented by Chemical Formula 7, and R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may each independently be a halogen atom.

The colorant may further comprise green pigments and yellow pigments.

Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may contain 1 to 10% by weight of (A) the binder resin, 1 to 10% by weight of the (B) photopolymerizable monomer, 0.1% to 5% by weight of the (C) photopolymerization initiator, 30% to 65% by weight of the (D) colorant, and 20% to 60% by weight of the (E) solvent.

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

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

Another embodiment provides a color filter including a photosensitive resin layer.

Other embodiments of the invention are included in the following detailed description.

The photosensitive resin composition according to the embodiment can achieve excellent brightness and chemical resistance, and can improve the residue on the organic layer (SiN _x ) after development when manufacturing a color filter pattern while using a practically conventional process physical properties without causing pattern tearing.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the invention is not limited thereto and the invention is defined by the scope of the claims.

As used herein, when no specific definition is otherwise provided, "substituted" refers to the replacement of at least one hydrogen of a functional group of the present invention by at least one substituent selected from the group consisting of: a halogen atom (F, Br, Cl, or I), hydroxy, nitro, cyano, amino (NH _{2 ,} NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different, and each independently is C1 to C10 alkyl), formamidino, hydrazine, hydrazone, carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, Substituted or unsubstituted alicyclic organic groups, substituted or unsubstituted aryl groups, and substituted or unsubstituted heterocyclyl groups.

As used herein, when a specific definition is not otherwise provided, "alkyl" refers to C1 to C20 alkyl, and specifically C1 to C15 alkyl, and "cycloalkyl" refers to C3 to C20 cycloalkyl , and specifically C3 to C18 cycloalkyl, "alkoxy" refers to C1 to C20 alkoxy, and specifically C1 to C18 alkoxy, and "aryl" refers to C6 to C20 aryl , and specifically C6 to C18 aryl, "alkenyl" refers to C2 to C20 alkenyl, and specifically C2 to C18 alkenyl, "alkylene" refers to C1 to C20 alkylene, and Specifically, C1 to C18 alkylene, and "arylidene" refers to C6 to C20 arylidene, and specifically C6 to C16 arylidene.

As used herein, when no specific definition is otherwise provided, the term "hetero" refers to the inclusion of at least one heteroatom selected from N, O, S, and P in a chemical formula.

As used herein, when a specific definition is not otherwise provided, "(meth)acrylate" refers to both "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic acid" ” and “methacrylic acid”.

In the chemical formulae of the present specification, unless a specific definition is provided otherwise, when a chemical bond is not drawn at the position where it should be given, the hydrogen bond is at the position.

As used herein, when a specific definition is not otherwise provided, "ethylenically unsaturated double bond" refers to a "carbon-carbon double bond", and ethylenically unsaturated monomer refers to a single ethylenically unsaturated double bond comprising a body.

As used herein, when a specific definition is not otherwise provided, "*" indicates a point to which the same or different atom or formula is linked.

[化學式2]

[化學式3]

The photosensitive resin composition according to the embodiment contains: (A) a binder resin containing an acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a phthalocyanine-containing binder A colorant for dyes; and (E) a solvent, wherein the acryl-based binder resin contains a structural unit represented by Chemical Formula 2, and the acryl-based binder resin further contains at least one selected from the structural units represented by Chemical Formula 1 and Chemical Formula 3. , and the acryl-based binder resin contains 5 to 25 wt % of the structural unit represented by Chemical Formula 2 based on the total amount of solids constituting the acryl-based binder resin. [Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

In Chemical Formula 1 to Chemical Formula 3, R ⁰ and R ¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, R ² is a substituted or unsubstituted C3 to C20 cycloalkyl group or A fused ring of two or more C3 to C20 cycloalkane rings, and L ¹ is a substituted or unsubstituted C1 to C20 alkylene.

As described above, the color filter produced by using the pigment-type photosensitive resin composition has limitations in brightness and contrast ratio due to the particle size of the pigment. In addition, color image sensor devices for image sensors require smaller dispersed particle diameters to form fine patterns. In order to meet the requirements, an attempt has been made to realize a color filter with improved brightness and contrast ratio by introducing a non-particle-forming dye in place of the pigment to prepare a photosensitive resin composition suitable for the dye.

Therefore, in the case where the photosensitive resin composition is used for a green filter, a general method for improving the brightness is to improve the color characteristics of the green dye, which does not mean that, in addition to the brightness, heat resistance properties, chemical resistance properties, residues Characteristics, pattern properties, and the like are not commonly improved, and thus there has been a need for a photosensitive resin composition for a (green) optical filter that can sustainably maintain stable pattern workability and high brightness characteristics. In addition, the problem of residues on the organic layer after development tends to be exacerbated as the dye content increases.

Therefore, the present inventors tried many times to find pigments with improved brightness characteristics and patternability, but could not ensure the effect of improving brightness and patternability by any novel pigments. Therefore, when a high content of green phthalocyanine dye is used, it may be mixed with a binder resin having a specific structure to obtain a high-brightness green photoresist, and at the same time, it can be ensured for use on the organic layer (SiN _x ) after development Process tolerance of residues A photosensitive resin composition with excellent properties and patternability is developed on the residues on the organic layer.

Hereinafter, each component is described in detail. ( A ) Binder resin

Specifically, the photosensitive resin composition according to the embodiment includes an acryl-based binder resin that includes "the structural unit represented by Chemical Formula 2" and simultaneously "the structural unit represented by Chemical Formula 1" " and/or "the structural unit represented by the chemical formula 3", and the structural unit represented by the chemical formula 2 is contained in an amount of 5 wt % to 25 wt % based on the total amount of solids constituting the acryl-based binder resin, and Thereby, even if the dye in the composition is contained in a high content, it is possible to resolve the phenomenon of residue on the organic layer after development very skillfully.

[化學式1-2]

[化學式1-3]

For example, the structural unit represented by Chemical Formula 1 may be at least one selected from the structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3. [Chemical formula 1-1]

[Chemical formula 1-2]

[Chemical formula 1-3]

For example, the structural unit represented by Chemical Formula 2 can be used to increase the acid value of the photosensitive resin composition. When the acryl-based binder resin is composed of the above-mentioned composition, an acid value can be imparted to the acryl-based binder resin and the effect of improving developability can be simultaneously achieved, and therefore regardless of the high dye content in the composition, when the organic Excellent residue properties on layers without pattern tearing. In the composition of the acryl-based binder resin as described above, when the structural unit represented by Chemical Formula 2 is contained in an amount of less than 5% by weight based on the total amount of solids constituting the acryl-based binder resin, Residue characteristics on the organic layer cannot be improved, however, when the structural unit represented by Chemical Formula 2 is contained in an amount of more than 25 wt % based on the total amount of solids constituting the acryl-based binder resin, pattern tearing may seriously occur. cracking phenomenon.

[化學式3-2]

For example, the structural unit represented by Chemical Formula 3 may be the structural unit represented by Chemical Formula 3-1 or Chemical Formula 3-2. [Chemical formula 3-1]

[Chemical formula 3-2]

In Chemical Formula 3-1 and Chemical Formula 3-2,

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

For example, the acryl-based binder resin may further include a structural unit represented by Chemical Formula 5. [Chemical formula 5]

In Chemical Formula 5, R ³ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocyclic group, or a substituted or unsubstituted C2-C20 heterocyclic group substituted or unsubstituted C6 to C20 aryl, and n is an integer from 0 to 5.

For example, the acryl-based adhesive resin may include 15 to 25 wt % of the structural unit represented by Chemical Formula 1-1, 5 to 15 % by weight of the structural unit represented by Chemical Formula 2, 25% to 35% by weight of the structural unit represented by Chemical Formula 3-1, 15% to 30% by weight of the structural unit represented by Chemical Formula 3-2, and 15% by weight to 25% by weight of the structural unit represented by Chemical Formula 5.

For example, the acryl-based binder resin may further include a structural unit represented by Chemical Formula 4. [Chemical formula 4]

In Chemical Formula 4, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L ² is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.

Even when the dye content is high, the structural unit represented by Chemical Formula 4 can realize a photosensitive resin composition having high brightness and excellent chemical resistance by imparting thermosetting properties to the acryl-based binder resin.

For example, the acryl-based binder resin may include a structural unit represented by Chemical Formula 1-2, a structural unit represented by Chemical Formula 1-3, a structural unit represented by Chemical Formula 2, and a structural unit represented by Chemical Formula 4, wherein the The structural unit represented by Chemical Formula 2 may be contained in an amount smaller than the amount of the structural unit represented by Chemical Formula 4 in terms of the total amount of solids constituting the acryl-based binder resin.

For example, the acryl-based adhesive resin may include 1 wt % to 10 wt % of the structural unit represented by Chemical Formula 1-2, 20 wt % to 50 % by weight of the structural unit represented by Chemical Formula 1-3, 15 to 25 wt % of the structural unit represented by Chemical Formula 2, and 30 to 50 wt % of the structural unit represented by Chemical Formula 4.

When the composition of the acryl-based binder resin is the same as above, the photosensitive resin composition including the composition has excellent brightness and chemical resistance, and can maintain the organic layer after development regardless of the high dye content excellent residue properties. In addition, the occurrence of pattern tearing can be prevented as much as possible.

The acryl-based binder resin may have a weight average molecular weight of 10,000 g/mol to 20,000 g/mol. For example, when the acryl-based binder resin includes structural units represented by Chemical Formula 1 to Chemical Formula 3 and Chemical Formula 5, it may have a weight average molecular weight of 10000 g/mol to 13000 g/mol. When the acryl-based binder resin includes structural units represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 4, the acryl-based binder resin may have a weight average molecular weight of 14,000 g/mol to 20,000 g/mol. When the weight-average molecular weight of the acryl-based binder resin is within the above-mentioned range, the photosensitive resin composition can have excellent physical and chemical properties, appropriate viscosity, and excellent adhesion with the substrate when manufacturing a color filter. Close contact properties.

The acrylic binder resin may have an acid value of 110 mg potassium hydroxide/gram to 130 mg potassium hydroxide/gram. When the acid value of the acryl-based binder resin is within the above range, the resolution of the pixel pattern can be improved.

For example, when the acryl-based binder resin is composed of v and the structural unit represented by Chemical Formula 5, in addition to the acryl-based binder resin, the photosensitive resin composition according to the embodiment may further include an epoxy-based binder Resin acts as a binder resin.

The epoxy-based binder resin can help ensure dispersion stability of dyes and pigments, which will be described later, and help to form pixels with desired resolution during the development process.

When the photosensitive resin composition according to the embodiment further contains an epoxy-based binder resin, heat resistance can be improved. The epoxy-based adhesive resin may include, for example, phenol novolac epoxy resin, tetramethyl biphenyl epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, or a combination thereof, But not limited to this.

For example, the epoxy-based adhesive resin may be represented by Chemical Formula X. [chemical formula X]

The epoxy equivalent of the epoxy-based adhesive resin may be 200 g/equivalent to 150 g/equivalent. When an epoxy-based binder resin having an epoxy equivalent within the above-mentioned range is used, the degree of curing of the formed pattern may be improved and it may be necessary to fix the dye in the structure in which the pattern is formed.

The acryl-based binder resin may be included in an amount greater than that of the epoxy-based binder resin.

The epoxy-based binder resin may be contained in an amount of 0.1% by weight to 1% by weight, for example, 0.1% by weight to 0.7% by weight, based on the total amount of the photosensitive resin composition.

For example, when the acryl-based binder resin is composed of structural units represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 4, in addition to the acryl-based binder resin, the photosensitive resin composition according to the embodiment may further include An acrylic resin having another structure is used as the binder resin.

The binder resin may be included in an amount of 1% by weight to 10% by weight, for example, 3% by weight to 10% by weight, based on the total amount of the photosensitive resin composition. When the binder resin within the above range is included, the brightness, heat resistance, and developability when manufacturing a color filter are improved, and the crosslinking property is improved to obtain excellent surface smoothness. ( D ) Colorants

The photosensitive resin composition according to the embodiment includes a phthalocyanine-based dye as a colorant, and the phthalocyanine-based dye can be represented by Chemical Formula 6 as a green dye. [Chemical formula 6]

在化學式7中， R²⁰ 和R²¹ 各自獨立地為經C1到C5烷基取代或未經C1到C5烷基取代的C1到C10烷基，以及 o和p各自獨立地為0到5的整數，前提為1 ≤ o + p ≤ 5。In Chemical Formula 6, R ⁴ to R ¹¹ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, R ¹² to R ¹⁹ are each independently a hydrogen atom, and at least one of R ⁴ to R ⁷ and at least one of R ⁸ to R ¹¹ are each independently represented by Chemical Formula 7, [Chemical Formula 7]

In Chemical Formula 7, R ²⁰ and R ²¹ are each independently a C1 to C10 alkyl group substituted or unsubstituted with a C1 to C5 alkyl group, and o and p are each independently an integer of 0 to 5 , provided that 1 ≤ o + p ≤ 5.

The compound represented by Chemical Formula 6 has excellent green spectral characteristics and high brightness. In addition, the compound represented by Chemical Formula 6 contains an aryloxy group represented by Chemical Formula 7, and the aryloxy group contains an alkyl group as a substituent, and the alkyl group is not substituted with an alkyl group or is substituted with an alkyl group, and thus may Excellent solubility in organic solvents

Either one of R ²⁰ and R ²¹ may be an unsubstituted alkyl group, and the other may be an isopropyl or tert-butyl-containing substituent at the terminal, such as tert-butyl. Thereby, the solubility in the organic solvent can be increased, and the brightness can be improved.

Each of o and p may each independently be an integer of 1. The aryloxy group represented by Chemical Formula 7 contains, as a substituent, two alkyl groups substituted or unsubstituted with an alkyl group (specifically, an unsubstituted alkyl group and an alkyl group substituted with an alkyl group), And thus, the aryloxy group may have better solubility in an organic solvent than in the case where one alkyl group is included as a substituent.

For example, Chemical Formula 7 may be represented by Chemical Formula 7-1. [Chemical formula 7-1]

In Chemical Formula 7-1, R ²⁰ is an alkyl-substituted or unsubstituted C1 to C10 alkyl group, and R ²¹ is an unsubstituted C1 to C10 alkyl group.

R ²⁰ may exist at the ortho position with respect to the oxygen atom constituting the aryloxy group, and R ²¹ may exist at the para position with respect to the oxygen atom constituting the aryloxy group. When the alkyl substituents are present in the ortho and para positions, respectively, with respect to the oxygen atom constituting the aryloxy group, this case has a favorable effect on solubility and brightness compared to other cases.

In addition, in Chemical Formula 6, R ⁴ to R ¹¹ are not hydrogen atoms, and R ¹² to R ¹⁹ are each independently a hydrogen atom, and thus the photosensitive resin composition according to the embodiment can be compared with phthalocyanines having different structures used alone The dye-like case has more improved brightness and chemical resistance.

For example, in Chemical Formula 6, R ⁶ and R ⁹ may each independently be represented by Chemical Formula 7, and R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may each independently be a halogen atom.

For example, green phthalocyanine dyes can be used in combination with auxiliary dyes.

Examples of the auxiliary dye may include triarylmethane-based dyes, anthraquinone-based dyes, benzylidene-based dyes, cyanine-based dyes, phthalocyanine-based dyes (having another structure), azaporphyrin-based dyes, indigo-based dyes, Dibenzopyran dyes.

The colorant may further comprise green pigments (dispersion) and yellow pigments (dispersion).

Pigments having excellent compatibility with green dyes such as phthalocyanine-based green dyes can be used as the yellow pigment dispersion. For example, the yellow pigment dispersion may have an amine value of 20 mg potassium hydroxide/gram to 60 mg potassium hydroxide/gram. Typically, yellow pigment dispersions have an amine value of 100 mg KOH/gram to 120 mg KOH/gram. When the amine value of the yellow pigment dispersion is limited as described above (limited to having a lower amine value than conventional amine values), compatibility with the aforementioned green dye is maximized, and brightness can be greatly improved.

Since the colorant has the above-mentioned composition, the photosensitive resin composition according to the embodiment can realize high brightness.

Examples of yellow pigments may be C.I. Pigment Yellow 11, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. , C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. , C.I. Pigment Yellow 185, C.I. Pigment Yellow 199, C.I. Pigment Yellow 215, C.I. Pigment Yellow 231, etc.

Examples of green pigments may be Green Pigments C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, and the like.

The pigments may be used alone or in a mixture of two or more, but are not limited thereto.

The pigment dispersion liquid may contain a pigment, a dispersant, and a dispersing resin. For example, the pigment dispersion may further contain a solvent.

The solvent of the pigment dispersion liquid may be ethylene glycol acetate, ethyl glycol ethyl ether, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, etc., and is desirably Propylene Glycol Methyl Ether Acetate.

The dispersing agent contributes to uniform dispersion of the pigment, and may contain a nonionic dispersing agent, an anionic dispersing agent, or a cationic dispersing agent. Specific examples may be polyalkylene glycol or its ester, polyoxyalkylene, polyol ester alkylene oxide addition product, alcohol alkylene oxide addition product, sulfonate, sulfonate, carboxylate, carboxylate acid salts, alkylamide alkylene oxide addition products, alkylamines, and may be used alone or in a mixture of two or more.

The dispersing resin may be an acryl-based resin containing a carboxyl group, and improves the stability of the pigment dispersion liquid and the pattern properties of the pixels.

Pigments can be used after pretreatment with water-soluble inorganic salts and humectants. When the pigment is used after pretreatment, the initial particle diameter of the yellow pigment can become finer.

The pretreatment can be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

The kneading may be performed at a temperature in the range of 40°C to 100°C, and the filtration and washing may be performed by filtering the pigment after washing off the inorganic salt with water or the like.

Examples of the water-soluble inorganic salt may be sodium chloride, potassium chloride, and the like, but are not limited thereto. Wetting agents can uniformly mix and pulverize pigments with water-soluble inorganic salts. Examples of humectants may include alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether; alcohols such as ethanol, isopropanol, butanol, hexanol, Cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol. These can be used alone or in combination of two or more.

The pigment may have an average particle diameter of 30 nm to 100 nm after kneading. When the average particle diameter of the pigment is within the above range, a fine pattern having excellent heat resistance and light resistance can be effectively formed.

The colorant may be included in an amount of 30% by weight to 65% by weight based on the total amount of the photosensitive resin composition. When a colorant within the above range is used, high brightness can be achieved in the desired color coordinates. For example, the phthalocyanine-based dye may be included in an amount of 30% by weight or more based on the total amount of the photosensitive resin composition. In general, in the case where the photosensitive resin composition has an extremely high dye content, problems such as undeveloped or residue on the organic layer after development due to poor developability are easily caused. However, in the photosensitive resin composition according to the embodiment, even if the dye content is 30 wt % or more based on the total amount of the composition, residue generation (one of the conventional problems) does not occur. This is because the acryl-based binder resin has the same composition as that described above. ( B ) Photopolymerizable monomers

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

Since the photopolymerizable monomer has an ethylenically unsaturated double bond, it is possible to form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure during pattern formation.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate (Meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate 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, tri(meth)acryloyloxyethyl phosphate, novolac epoxy (meth)acrylate, and the like.

Commercial examples of the photopolymerizable monomer are as follows. Monofunctional (meth)acrylates may include Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic Chemical Ind., Ltd.), etc. Examples of difunctional (meth)acrylates may include Aronix M-210 ^® , M-240 ^® , M-6200 ^® (Toa Synthetic Chemical Industry Co., Ltd.); KAYARAD HDDA ^® , HX-220 ^® , R-604 ^® ( Nippon Kayaku Co., Ltd.); V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of trifunctional (meth)acrylates may include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M-8060 ^® (East Asia Synthetic Chemical Industry Co., Ltd.); KAYARAD TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA120 ^® (Nihon Kayaku Co., Ltd.); V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.), etc. These can be used alone or in a mixture of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to improve developability.

The photopolymerizable monomer may be included in an amount of 1 wt % to 10 wt % based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer within the above range is contained, curing occurs sufficiently during exposure in the pattern formation process to provide excellent reliability and excellent developability by an alkaline developer. ( C ) Photopolymerization initiator

The photopolymerization initiator may include acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, and the like.

Examples of the acetophenone-based compound may include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (Methylthio)phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, etc. .

Examples of the benzophenone-based compound may include benzophenone, benzoylbenzoic acid, benzoylbenzoic acidmethyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, etc.

Examples of the thioxanthone compound may include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone, etc.

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

Examples of triazine compounds may 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-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine oxazine, 2-4-bis(trichloromethyl)-6-pipronyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine azine etc.

Examples of the oxime-based compound may include O-oxime-based compound, 2-(O-benzyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1- (O-acetoxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]ethanone, O-ethoxycarbonyl-α- Hydroxyamino-1-phenylpropan-1-one, etc. Specific examples of O-oxime compounds may include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl) phenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate , 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, etc.

In addition to the compounds, the photopolymerization initiator may include oxazole-based compounds, diketone-based compounds, pericynium borate-based compounds, diazo-based compounds, imidazole-based compounds, biimidazole-based compounds, and the like.

Photopolymerization initiators can be used together with sensitizers that are capable of causing chemical reactions by absorbing light and becoming an excited state and then transferring its energy.

Examples of the sensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

The photopolymerization initiator may be contained in an amount of 0.1% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator within the range is included, excellent reliability can be ensured due to sufficient curing during exposure during pattern formation, and transmittance deterioration can be prevented due to the non-reactive initiator. ( E ) Solvent

The solvent may be a material compatible with but not reactive with the binder resin, photopolymerizable monomer, photopolymerization initiator, and colorant.

Examples of the solvent may include: alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene glycol methyl ether, ethyl ether Glycol ethyl ether, propylene glycol methyl ether, etc.; ethylene glycol ethyl acetate, such as methyl ethylene glycol ethyl ether, ethyl glycol ethyl acetate, diethyl glycol ethyl acetate, etc.; carbitol, such as methyl ethyl acetate Base Carbitol, Diethyl Carbitol, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Dimethyl Ether, Diethylene Glycol Methyl Ether, Diethylene Glycol Diethylene Glycol Diethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons, such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone , 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters, such as acetic acid Ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactate, such as methyl lactate, ethyl lactate, etc.; alkyl glycolate, such as methyl glycolate, ethyl glycolate, butyl glycolate Esters, etc.; alkoxyalkyl acetates, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, etc.; 3 -Hydroxyalkyl propionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; 3-alkoxyalkyl propionate, such as methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; 2-hydroxyalkyl propionate, such as methyl 2-hydroxypropionate, 2-hydroxypropionate Ethyl propionate, propyl 2-hydroxypropionate, etc.; 2-alkoxyalkyl propionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-ethoxy propionate, etc.; 2-hydroxy-2-methyl alkyl propionate, such as methyl 2-hydroxy-2-methyl propionate, 2-hydroxy-2 -ethyl methylpropionate, etc.; 2-alkoxy-2-methylalkylpropionate, such as methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate Ethyl propionate, etc.; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, methyl 2-hydroxy-3-methyl Butyrate, etc; Amine, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, octanoic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol ether Phenyl acetate, etc. These can be used alone or in a mixture of two or more.

In view of miscibility and reactivity, glycol ethers, such as ethylene glycol monoethyl ether, etc.; glycol alkyl ether acetates, such as ethylene glycol ethyl ether ethyl ether, etc.; esters, such as propionic acid, can be desirably used 2-hydroxyethyl ester, etc.; diethylene glycol, such as diethylene glycol monomethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

The solvent is used in the remainder, for example, 20% by weight to 60% by weight, based on the total amount of the photosensitive resin composition. When the solvent within the above range is contained, a coating film having excellent applicability of the photosensitive resin composition and excellent flatness can be obtained. ( F ) Other additives

The photosensitive resin composition may further include other additives, such as malonic acid, 3-amino-1,2-propanediol, silane coupling agents, leveling agents, fluorine surfactants, radical polymerization initiators or combinations thereof, In order to prevent smears or spots during coating, improve leveling performance or prevent residue formation due to undevelopment.

Examples of silane-based coupling agents may be trimethoxysilylbenzoic acid, gamma methacryloylpropoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma isocyanatepropyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-epoxycyclohexylethyltrimethoxysilane, etc. These can be used alone or in a mixture of two or more.

Examples of fluorosurfactants may be commercially available fluorosurfactants such as BM-1000® and BM- ^{1100® (} BM Chemie Inc.); MEGAFACE ^F142D® , ^F172® , F 173 ^® and F 183 ^® (Dainippon Ink Kagaku Kogyo Co., Ltd.; FULORAD FC-135 ^® , FULORAD FC-170C ^® , FULORAD FC-430 ^® and FULORAD FC-431 ^® (Sumitomo 3M Co., Ltd.); SURFLON S-112 ^® , SURFLON S-113 ^® , SURFLON S-131 ^® , SURFLON S-141 ^® and SURFLON S-145 ^® (Asahi Glass Co., Ltd. (Asahi Glass Co., Ltd.); and SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® and SF-8428 ^® etc. (Toray Silicone Co., Ltd .)).

The amount of additives used can be controlled depending on the desired properties.

Another embodiment provides a photosensitive resin layer manufactured using the aforementioned photosensitive resin composition.

Another embodiment provides a color filter including a photosensitive resin layer.

The method of manufacturing the color filter is as follows.

The above photosensitive resin composition is coated on a glass substrate by an appropriate method, such as spin coating, roll coating, spray coating, etc., to form a resin composition layer of 0.5 μm to 10 μm thick.

Subsequently, the substrate having the resin composition layer is irradiated with light to form a desired pattern for the color filter. As a light source for irradiation, UV, electron beams, or X-rays may be used, and for example, UV in a region of 190 nm to 450 nm, specifically, 200 nm to 400 nm may be radiated. During the irradiation process, a photoresist mask may further be used. After performing the irradiation process in this way, the resin composition layer irradiated with the light source is processed with a developing solution. At this time, the unexposed portion of the resin composition layer is dissolved to form a pattern necessary for the color filter. By repeating this process for a large number of desired pigments, a color filter with the desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is cured by heating again or by irradiation with actinic rays, crack resistance and solvent resistance can be improved.

Another embodiment provides a display device or a complementary metal-oxide semiconductor (CMOS) image sensor (complementary metal-oxide semiconductor image sensor; CIS) including a color filter.

Hereinafter, the present invention is explained in more detail with reference to Examples. However, these examples should not be construed as limiting the scope of the present invention in any sense. ( Preparation of Acrylic Binder Resin ) Synthesis Example 1 to Synthesis Example 5 and Comparative Synthesis Example 1 to Comparative Synthesis Example 3

7 parts by weight (based on the total amount (100 parts by weight) of the monomers used for polymerization excluding AIBN) of AIBN as an initiator was placed in a flask equipped with a cooler and a stirring bar, according to the The monomers used for polymerization were sequentially added thereto, and 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added thereto based on 100 parts by weight of the total weight of the monomers. solvent and initiator, and then slowly stirred under a nitrogen atmosphere. The reaction solution was heated to 85°C and stirred for 6 hours to polymerize the acrylamide-based binder resin. The acryl-based binder resin solution obtained in the above-mentioned method had a solid concentration of 30% by weight, wherein the weight-average molecular weight thereof was reduced to that of polystyrene, which was obtained by using gel permeation chromatography (Gel Permeation Chromatography; GPC). ) to measure. [Table 1] (unit: % by weight, based on solid content) Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Methacrylic acid (chemical formula 1) 20 20 20 20 20 20 15 twenty two Dicyclopentyl methacrylate (chemical formula 3) 30 30 33 29 25 35 25 35 Phenylmaleimide (chemical formula 5) 15 15 17 15 15 20 15 twenty three Cyclohexyl methacrylate (chemical formula 3) 25 20 25 20 15 25 19 16 4-Hydroxybutyl acrylate (chemical formula 2) 10 15 5 16 25 - 26 4 Weight Average Molecular Weight (g/mol) 11400 12200 12500 12000 11800 8530 9200 10280 Synthesis Example 6 to Synthesis Example 10 and Comparative Synthesis Example 4 and Comparative Synthesis Example 5

10 parts by weight (based on the total amount (100 parts by weight) of the monomers used for polymerization excluding AIBN) of AIBN as an initiator was placed in a flask equipped with a cooler and a stirring bar, as shown in Table 2. The monomers used for polymerization are sequentially added thereto, and based on 100 parts by weight of the total weight of the monomers, 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) solvent and an initiator are added thereto, And then slowly stirred under nitrogen atmosphere. The reaction solution was heated to 85°C and stirred for 6 hours to polymerize the acrylamide-based binder resin. The acrylonitrile-based binder resin solution obtained in the above-described method had a solid concentration of 30% by weight, wherein its weight average molecular weight was a molecular weight reduced to that of polystyrene, which was measured by using gel permeation chromatography (GPC). [Table 2] (unit: % by weight, based on solid content) Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Comparative Synthesis Example 4 Comparative Synthesis Example 5 Acrylic (chemical formula 1) 5 5 5 10 5 10 5 4-Hydroxybutyl acrylate (chemical formula 2) 15 15 25 5 25 4 26 Cyclohexyl methacrylate (chemical formula 3) 50 Methmethacrylic acid (chemical formula 1) 50 30 20 50 20 50 20 Glycidyl methacrylic acid (chemical formula 4) 30 50 50 35 36 49 Weight Average Molecular Weight (g/mol) 14800 15000 15200 15000 17000 14500 15000 ( Preparation of Photosensitive Resin Composition ) Examples 1 to 10 and Comparative Examples 1 to 6

The photosensitive resin compositions according to Examples 1 to 10 and Comparative Examples 1 to 6 were prepared to have each of the compositions shown in Table 3 and Table 4 by using the components described below.

Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent is added thereto, and then sufficiently stirred until the photopolymerization initiator is completely dissolved (30 minutes or more). Subsequently, an acryl-based binder resin and a photopolymerizable monomer were sequentially added thereto, and then stirred again for about 1 hour. Next, a colorant was added thereto, and an antioxidant and other additives were added thereto, and then finally stirred for 2 hours and more, thereby preparing a photosensitive resin composition.

（E）溶劑 丙二醇甲醚乙酸酯（PGMEA，西格瑪-奧德裏奇公司（Sigma-Aldrich Corporation）） （F）其它添加劑 氟類表面活性劑（F-554，迪愛生有限公司（DIC Co., Ltd.）） [表3] （單位：重量%）   實例1 實例2 實例3 實例4 實例5 比較例1 比較例2 比較例3 （A） 黏合劑樹脂 A-1 7.91               A-2   7.91             A-3     7.91           A-4       7.91         A-5         7.91       A-11           7.91     A-12             7.91   A-13               7.91 A-16 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 （B）光可聚合單體 B-1 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 B-2 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 （C）光聚合引發劑 C-1 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 C-2 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 （D）著色劑 D-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 D-2 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 D-3 30.22 30.22 30.22 30.22 30.22 30.22 30.22 30.22 （E）溶劑 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 （F）其它添加劑 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 [表4] （單位：重量%）   實例6 實例7 實例8 實例9 實例10 比較例4 比較例5 比較例6 （A） 黏合劑樹脂 A-6 5.20               A-7   5.20             A-8     5.20           A-9       5.20         A-10         5.20       A-14           5.20     A-15             5.20   A-16               5.20 A-17 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 （B）光可聚合單體 B-1 4.90 4.90 4.90 4.90 4.90 4.90 4.90 4.90 B-2 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 （C）光聚合引發劑 C-1 0.79 0.79 0.79 0.79 0.79 0.79 0.79 0.79 C-2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 （D） 著色劑 D-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 D-2 17.80 17.80 17.80 17.80 17.80 17.80 17.80 17.80 D-3 30.20 30.20 30.20 30.20 30.20 30.20 30.20 30.20 （E）溶劑 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 （F）其它添加劑 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 評估 1 ： 顏色特性 The components used to prepare the photosensitive resin composition are as follows. (A) Binder Resin (A-1) Acrylic Binder Resin (Synthesis Example 1) (A-2) Acrylic Binder Resin (Synthesis Example 2) (A-3) Acrylic Binder Resin ( Synthesis Example 3) (A-4) Acrylic Binder Resin (Synthesis Example 4) (A-5) Acrylic Binder Resin (Synthesis Example 5) (A-6) Acrylic Binder Resin (Synthesis Example 6) (A-7) Acrylic Binder Resin (Synthesis Example 7) (A-8) Acrylic Binder Resin (Synthesis Example 8) (A-9) Acrylic Binder Resin (Synthesis Example 9) (A-10) Acrylic Binder Resin (Synthesis Example 10) (A-11) Acrylic Binder Resin (Comparative Synthesis Example 1) (A-12) Acrylic Binder Resin (Comparative Synthesis Example 2) (A-13) Acrylic Binder Resin (Comparative Synthesis Example 3) (A-14) Acrylic Binder Resin (Comparative Synthesis Example 4) (A-15) Acrylic Binder Resin (Comparative Synthesis Example 5) ) (A-16) Epoxy adhesive resin (epoxy equivalent: 177 g/equivalent) (EHPE-3150, DAICEL CHEMICAL) (A-17) Acrylic adhesive resin (NPR-5216) , Miwon) (B) Photopolymerizable monomer (B-1) DPHA (Nippon KAYAKU) (B-2) ABPE-20 (Shin-nakamura) (C) Photopolymerization initiator (C-1) SPI-03 (Samyang Corp.) (C-2) IRG369 (BASF) (D) Colorant (D-1) CI Pigment Green 58 (Sanyo (SANYO company) (D-2) CI Pigment Yellow 138 (Sanyo Company) (20 mg potassium hydroxide/g to 60 mg potassium hydroxide/g amine value) (D-3) Phthalophane represented by chemical formula P Cyanine green dye (Kyungin Corporation) [chemical formula P]

(E) Solvent Propylene Glycol Methyl Ether Acetate (PGMEA, Sigma-Aldrich Corporation) (F) Other Additives Fluorosurfactant (F-554, DIC Co., Ltd.)) [Table 3] (unit: % by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Binder resin A-1 7.91 A-2 7.91 A-3 7.91 A-4 7.91 A-5 7.91 A-11 7.91 A-12 7.91 A-13 7.91 A-16 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 (B) Photopolymerizable Monomer B-1 4.92 4.92 4.92 4.92 4.92 4.92 4.92 4.92 B-2 0.37 0.37 0.37 0.37 0.37 0.37 0.37 0.37 (C) Photopolymerization initiator C-1 0.78 0.78 0.78 0.78 0.78 0.78 0.78 0.78 C-2 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 (D) Colorants D-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 D-2 17.79 17.79 17.79 17.79 17.79 17.79 17.79 17.79 D-3 30.22 30.22 30.22 30.22 30.22 30.22 30.22 30.22 (E) Solvent 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 (F) Other additives 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 [Table 4] (unit: % by weight) Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 4 Comparative Example 5 Comparative Example 6 (A) Binder resin A-6 5.20 A-7 5.20 A-8 5.20 A-9 5.20 A-10 5.20 A-14 5.20 A-15 5.20 A-16 5.20 A-17 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 (B) Photopolymerizable Monomer B-1 4.90 4.90 4.90 4.90 4.90 4.90 4.90 4.90 B-2 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 (C) Photopolymerization initiator C-1 0.79 0.79 0.79 0.79 0.79 0.79 0.79 0.79 C-2 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 (D) Colorants D-1 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 D-2 17.80 17.80 17.80 17.80 17.80 17.80 17.80 17.80 D-3 30.20 30.20 30.20 30.20 30.20 30.20 30.20 30.20 (E) Solvent 34.50 34.50 34.50 34.50 34.50 34.50 34.50 34.50 (F) Other additives 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Evaluation 1 : Color Properties

By using a coater (Opticoat MS-A150, Mikasa Co., Ltd.), the samples according to Examples 1 to 10 and Comparative Example 1 to The photosensitive resin composition of Comparative Example 6 was prebaked on a 90° C. hot plate for 2 minutes. Subsequently, the front surface of the coated photosensitive resin composition was exposed by using a high pressure mercury lamp having a total wavelength of 365 nm under an exposure condition of 40 mJ/cm 2 , and then baked in an oven at 230° C. for 20 minutes to obtain a sample. The brightness of the samples was measured by using the MCPD 3000 equipment before and after the oven bake, and the results are shown in Table 5. Evaluation 2 : Chemical Resistance

After immersing the sample obtained under the same conditions as in Evaluation 1 in an N-methylpyrrolidone (NMP) solution for 10 minutes at room temperature, by using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd. (Otsuka Electronics Co., Ltd.)) transmission spectra of the samples before and after immersion were obtained and used to calculate ΔEab* according to Equation 1, and the results are shown in Table 5. [Equation 1] ΔEab* =√{(ΔL*) ² +(Δa*) ² +(Δb*) ² } (The smaller the value of ΔEab*, the better the chemical resistance) Evaluation 3 : Residue characteristics

Coating and developing according to Example 1 to Example 10 by preparing a red patterned substrate on lower 1000 Angstrom _SiNx -coated glass and subjecting it to extreme ultra violet (EUV) impurity removal by using excimer UV stripping With each of the green photosensitive resin compositions of Comparative Examples 1 to 6, the residue evaluation was performed by observing the residue on the SiN _x substrate with an optical microscope, and the results are shown in Table 5 and FIGS. 1 to 3 . <Evaluation Criteria for Residue Properties on Organic Layer> ○: No residue on the organic layer under an optical microscope ×: Residue on the organic layer under an optical microscope Evaluation 4 : Patternability

Whether or not the pattern formed in the sample obtained under the same conditions as Evaluation 1 was measured using an optical microscope with 500x zoom, and the results are shown in Table 5 and FIGS. 4 to 7 . <Patternability Evaluation Criteria> ○: The pattern was not torn but formed into a single outline ×: The pattern was torn and formed into a 2-step outline [Table 5] brightness(%) Chemical resistance (ΔEab*) Residue properties patterning Example 1 99.9 1.5 ○ ○ Example 2 99.7 1.4 ○ ○ Example 3 99.9 1.3 ○ ○ Example 4 99.8 1.4 ○ ○ Example 5 99.8 1.4 ○ ○ Example 6 100.0 1.3 ○ ○ Example 7 100.2 1.5 ○ ○ Example 8 100.2 1.6 ○ ○ Example 9 100.3 1.5 ○ ○ Example 10 99.7 2.2 ○ ○ Comparative Example 1 98.7 2.3 × ○ Comparative Example 2 98.9 2.3 × × Comparative Example 3 99.2 2.2 × ○ Comparative Example 4 99.3 2.4 × × Comparative Example 5 99.2 2.4 × × Comparative Example 6 99.5 2.6 × ×

Referring to Table 5 and FIGS. 1 to 7 , the photosensitive resin compositions according to Examples 1 to 10 exhibited high brightness and excellent chemical resistance as compared with the photosensitive resin compositions according to Comparative Examples 1 to 6 And at the same time, excellent residue characteristics and pattern characteristics are exhibited on the organic layer.

While this invention has been described in connection with what are presently considered to be practical example embodiments, it is to be understood that this invention is not limited to the disclosed embodiments, but on the contrary, this invention is intended to cover the spirit and scope encompassed by the appended claims Various modifications and equivalent arrangements within. Accordingly, the foregoing embodiments should be understood to be exemplary and not to limit the present invention in any way.

without

1 is an optical microscope photograph for determining the characteristics of residues on an organic layer (SiN _x ) after developing the photosensitive resin composition according to Example 1. FIG. 2 is an optical microscope photograph for determining the characteristics of the residue on the organic layer (SiN _x ) after developing the photosensitive resin composition according to Comparative Example 3. FIG. 3 is an optical microscope photograph for determining the characteristics of the residue on the organic layer (SiN _x ) after developing the photosensitive resin composition according to Comparative Example 1. FIG. 4 and 5 are optical micrographs of patterns obtained by using the photosensitive resin composition according to Example 1. 6 and 7 are optical micrographs of patterns obtained by using the photosensitive resin composition according to Comparative Example 2.

Claims (17)

A photosensitive resin composition, comprising: a binder resin including an acryl-based binder resin; a photopolymerizable monomer; a photopolymerization initiator; a colorant including a phthalocyanine-based dye; and a solvent wherein the acryl-based binder The agent resin includes a structural unit represented by Chemical Formula 2, the acryl-based binder resin further includes at least one selected from the structural units represented by Chemical Formula 1 and Chemical Formula 3, and the solid that constitutes the acryl-based binder resin The acryl-based binder resin contains 5 wt % to 25 wt % of the structural unit represented by Chemical Formula 2: [Chemical Formula 1]

[Chemical formula 2]

[Chemical formula 3]

wherein, in Chemical Formulas 1 to 3, R ⁰ and R ¹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and R ² is a substituted or unsubstituted C3 to C20 cycloalkane or a fused ring of two or more C3 to C20 cycloalkane rings, and L ¹ is a substituted or unsubstituted C1 to C20 alkylene. The photosensitive resin composition according to claim 1, wherein the phthalocyanine-based dye is contained in an amount of 30% by weight or more based on the total amount of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 is at least one selected from the group consisting of structural units represented by Chemical Formula 1-1 to Chemical Formula 1-3: [Chemical Formula 1-1]

[Chemical formula 1-2]

[Chemical formula 1-3]

. The photosensitive resin composition according to claim 3, wherein the structural unit represented by Chemical Formula 3 is represented by Chemical Formula 3-1 or Chemical Formula 3-2: [Chemical Formula 3-1]

[Chemical formula 3-2]

Wherein, in Chemical Formula 3-1 and Chemical Formula 3-2, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group. The photosensitive resin composition according to claim 3, wherein the acryl-based binder resin further comprises a structural unit represented by Chemical Formula 4: [Chemical Formula 4]

Wherein, in Chemical Formula 4, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, and L ² is a single bond or a substituted or unsubstituted C1 to C20 alkylene group. The photosensitive resin composition according to claim 4, wherein the acryl-based binder resin further comprises a structural unit represented by Chemical Formula 5: [Chemical Formula 5]

wherein, in Chemical Formula 5, R ³ is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocyclic group or substituted or unsubstituted C6 to C20 aryl, and n is an integer from 0 to 5. The photosensitive resin composition according to claim 5, wherein The acryl-based binder resin includes the structural unit represented by Chemical Formula 1-2, the structural unit represented by Chemical Formula 1-3, the structural unit represented by Chemical Formula 2, and the structural unit represented by Chemical Formula 4. structural unit, and The structural unit represented by Chemical Formula 2 is contained in an amount smaller than the amount of the structural unit represented by Chemical Formula 4, based on the total amount of solids constituting the acryl-based binder resin. The photosensitive resin composition according to claim 5, wherein In terms of the total amount of solids constituting the acryl-based binder resin, The acryl-based binder resin contains 1% to 10% by weight of the structural unit represented by Chemical Formula 1-2; 20% to 50% by weight of the structural unit represented by Chemical Formula 1-3; 15% to 25% by weight of the structural unit represented by Chemical Formula 2; and 30 wt % to 50 wt % of the structural unit represented by Chemical Formula 4. The photosensitive resin composition according to claim 6, wherein In terms of the total amount of solids constituting the acryl-based binder resin, The acryl-based binder resin contains 15% to 25% by weight of the structural unit represented by Chemical Formula 1-1; 5% to 15% by weight of the structural unit represented by Chemical Formula 2; 25% to 35% by weight of the structural unit represented by Chemical Formula 3-1; 15% to 30% by weight of the structural unit represented by Chemical Formula 3-2; and 15 wt % to 25 wt % of the structural unit represented by Chemical Formula 5. The photosensitive resin composition according to claim 1, wherein the acryl-based binder resin has a weight average molecular weight of 10,000 g/mol to 20,000 g/mol. The photosensitive resin composition according to claim 1, wherein the phthalocyanine-based dye is represented by Chemical Formula 6: [Chemical Formula 6]

wherein, in Chemical Formula 6, R ⁴ to R ¹¹ are each independently a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group, or a substituted or unsubstituted C6 to C20 aryloxy group, and R ¹² to R ¹⁹ is each independently a hydrogen atom, and at least one of R ⁴ to R ⁷ and at least one of R ⁸ to R ¹¹ are each independently represented by Chemical Formula 7, [Chemical Formula 7]

wherein, in Chemical Formula 7, R ²⁰ and R ²¹ are each independently an unsubstituted or C1 to C10 alkyl group substituted with a C1 to C5 alkyl group, and o and p are each independently an integer of 0 to 5, provided that 1 ≤ o + p ≤ 5. The photosensitive resin composition according to claim 11, wherein in Chemical Formula 6, R ⁶ and R ⁹ are each independently represented by Chemical Formula 7, and R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹⁰ , and R ¹¹ Each is independently a halogen atom. The photosensitive resin composition according to claim 1, wherein the colorant further comprises a green pigment and a yellow pigment. The photosensitive resin composition according to claim 1, wherein Based on the total amount of the photosensitive resin composition, The photosensitive resin composition contains 1% to 10% by weight of the binder resin; 1% to 10% by weight of the photopolymerizable monomer; 0.1% to 5% by weight of the photopolymerization initiator; 30% to 65% by weight of the colorant; and 20% to 60% by weight of the solvent. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, and a fluorine-based surfactant additives, free radical polymerization initiators, or combinations thereof. A photosensitive resin layer produced using the photosensitive resin composition according to any one of Claims 1 to 15. A color filter comprising the photosensitive resin layer as claimed in claim 16.

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