KR102196844B1 - Photosensitive resin composition and photosensitive resin layer using the same and color filter - Google Patents

Abstract

(A) acrylic binder resin; (B) a colorant comprising a green dye and a yellow pigment dispersion; (C) photopolymerizable monomer; (D) photoinitiator; And (E) a photosensitive resin composition containing a solvent, and a color filter manufactured using the same.

Description

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

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

Recently, as the widespread use of large-screen liquid crystal display devices has increased, the demand for new performance improvement for liquid crystal display devices is increasing. Among the parts of liquid crystal display devices, color filters are the most important to realize color and are intended to increase process margin for productivity. Research is ongoing.

In addition, in the case of large-screen liquid crystal displays, the colorant concentration of the photosensitive resin composition is increasing when manufacturing color filters to increase color purity, and to increase productivity and yield in the manufacturing process, a photosensitive resin composition with excellent sensitivity is required to lower the developing speed and to increase the sensitivity even at small exposure doses. Has become.

A color filter using a photosensitive resin composition can be prepared by coating three or more colors on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, or a pigment dispersion method, and recently, a pigment dispersion method is widely used.

On the other hand, in a color filter made of a pigment type photosensitive resin composition, there is a limitation in that the brightness and contrast ratio are lowered due to the pigment particle size and the aggregation of the pigment particles. In order to improve this limitation, attempts are underway to use a dye-type photosensitive resin composition in which a dye having no particles or having a very small primary particle diameter compared to the pigment dispersion is introduced. However, in the case of a dye-type photosensitive resin composition, it is difficult to commercialize it due to weak heat resistance, light resistance and chemical resistance.

One embodiment is to provide a photosensitive resin composition capable of securing high luminance characteristics.

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.

One embodiment is (A) an acrylic binder resin; (B) a colorant comprising a green dye and a yellow pigment dispersion; (C) a photopolymerizable monomer represented by the following formula (2); (D) photoinitiator; And (E) a solvent, wherein the green dye provides a photosensitive resin composition comprising a core including a compound represented by Formula 1 below and a shell surrounding the core.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[Formula 2]

In Chemical Formula 2,

R ⁵ to R ¹⁰ are each independently represented by the following formula (3),

[Formula 3]

In Chemical Formula 3,

n is an integer from 0 to 2.

The R ¹ and R ³ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ² and R ⁴ are each independently a C1 to C10 alkyl group or a C3 to C10 It may be a C6 to C20 aryl group substituted with a cycloalkyl group.

The compound represented by Formula 1 may be represented by any one selected from the group consisting of compounds represented by Formula 1-1 to Formula 1-8 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

The cell may be represented by the following Chemical Formula 4 or Chemical Formula 5.

[Formula 4]

[Formula 5]

(In Chemical Formula 4 and Chemical Formula 5,

L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group)

Each of L ¹ to L ⁴ may be independently a substituted or unsubstituted C1 to C10 alkylene group.

The cell may be represented by the following Formula 4-1 or Formula 5-1.

[Formula 4-1]

[Chemical Formula 5-1]

The cell may have a cage width of 6.5 Å to 7.5 Å.

The length of the core may be 1nm to 3nm.

The core may have a maximum absorption peak at a wavelength of 530nm to 680nm.

The core-shell dye may be represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

The core-shell dye may include the core and the shell in a molar ratio of 1:1.

The yellow pigment dispersion comprises a yellow pigment, a dispersant and a dispersion resin, the dispersant has an amine value of 30 mgKOH/g to 50 mgKOH/g, and the dispersion resin is 110 mgKOH/g to 130 mgKOH/g It may have an acid value of.

The acrylic binder resin may include all structural units represented by Chemical Formulas 22 to 26 below.

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

In Chemical Formulas 22 to 26,

R ¹¹ and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹² is a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁷ is a substituted or unsubstituted C11 to C20 alkyl group,

L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group.

With respect to the total amount of the acrylic binder resin, the structural unit represented by Formula 22 is included in 20% to 30% by weight, the structural unit represented by Formula 23 is included in 15% to 25% by weight, and the formula The structural unit represented by 24 is included in 5% to 10% by weight, the structural unit represented by Chemical Formula 25 is included in 30% to 45% by weight, and the structural unit represented by Formula 26 is 5% by weight It may be included in to 15% by weight.

The acrylic binder resin may have a double bond equivalent weight of 500g/eq to 350g/eq.

The photosensitive resin composition may further include an epoxy-based binder resin.

The epoxy-based binder resin may include a compound represented by Formula 27 below.

[Formula 27]

The epoxy-based binder resin may have an epoxy equivalent of 200 g/eq to 150 g/eq.

The acrylic binder resin may be included in an amount higher than that of the epoxy binder resin.

The photosensitive resin composition, based on the total amount of the photosensitive resin composition, the (A) acrylic binder resin 1% to 7% by weight; 3% to 15% by weight of the colorant (B); 2% to 8% by weight of the (C) photopolymerizable monomer; (D) 1% to 3% by weight of the photopolymerization initiator; And (E) may include 60% to 90% by weight of the solvent.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; Radical polymerization initiator; Or it may further include an additive of a combination thereof.

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.

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

The photosensitive resin composition according to an embodiment can secure color reproduction, exposure sensitivity and fine patterns when manufacturing a color filter pattern while using a conventional process as it is, have excellent heat resistance, and can greatly increase luminance characteristics.

1 is a view showing the cage width of the shell represented by Chemical Formula 5-1.

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, "substituted" to "substituted" means that at least one hydrogen atom in the functional groups of the present invention is a halogen atom (F, Cl, Br or I), a hydroxy group, a nitro group, a cyano group, an amino group ( NH ₂ , NH (R ²⁰⁰ ) or N (R ²⁰¹ ) (R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different from each other, and each independently a C1 to C10 alkyl group), an amidino group, Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, And it means substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, “alkyl group” refers to a C1 to C20 alkyl group, specifically C1 to C15 alkyl group, and “cycloalkyl group” refers to a C3 to C20 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "alkoxy group" refers to a C1 to C20 alkoxy group, specifically C1 to C18 alkoxy group, and "aryl group" refers to a C6 to C20 aryl group, specifically C6 to It means a C18 aryl group, and "alkenyl group" means a C2 to C20 alkenyl group, specifically C2 to C18 alkenyl group, and "alkylene group" means a C1 to C20 alkylene group, specifically C1 To C18 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

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

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

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

The photosensitive resin composition according to an embodiment includes (A) an acrylic binder resin; (B) a colorant comprising a green dye and a yellow pigment dispersion; (C) a photopolymerizable monomer represented by the following formula (2); (D) photoinitiator; And (E) a solvent. In addition, the green dye is composed of a core including a compound represented by the following formula (1) and a shell surrounding the core.

[Formula 1]

In Formula 1,

R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,

[Formula 2]

In Chemical Formula 2,

R ⁵ to R ¹⁰ are each independently represented by the following formula (3),

[Formula 3]

In Chemical Formula 3,

n is an integer from 0 to 2.

Although general luminance improvement was progressed in the direction of improvement of green pigments and yellow pigments, there was a limitation in improving luminance only by simple pigment improvement. However, according to one embodiment, by improving the green dye and using it with a photopolymerizable monomer that affects the degree of curing, the effect of improving brightness can be maximized. The photopolymerizable monomer used in the photosensitive resin composition according to the embodiment is represented by Formula 2, which is capable of controlling the degree of curing, unlike dipentaerythritol hexaacrylate (DPHA), etc. When used together with a green dye, it can contribute to maximizing brightness.

Hereinafter, each component will be described in detail.

(B) colorant

The colorant used in the photosensitive resin composition according to the embodiment includes a green dye and a yellow pigment dispersion.

The green dye has a core-shell structure, and the core may include the compound represented by Chemical Formula 1. Specifically, a coating layer may be formed while the shell surrounds the compound represented by Chemical Formula 1.

The compound represented by Formula 1 is a compound having excellent green spectral properties and a high molar extinction coefficient, and is suitable for use as a green dye. However, after manufacturing a color resist with inferior durability compared to the pigment, a decrease in luminance may occur during the baking process. In one embodiment, due to the structure in which the shell corresponding to the macrocyclic compound surrounds the compound represented by Formula 1, that is, a structure in which the compound represented by Formula 1 exists inside the macro ring forming the shell By having a, it is possible to improve the durability, and accordingly, it is possible to implement a color filter of high luminance.

In Formula 1, R ¹ and R ³ may each independently be a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ² and R ⁴ are each independently a C1 to C10 alkyl group Or it may be a C6 to C20 aryl group substituted with a C3 to C10 cycloalkyl group. For example, when R ² and/or R ⁴ is a C6 to C20 aryl group substituted with a C1 to C10 alkyl group, the R ² and/or R ⁴ is a C6 to C20 aryl group substituted with a substituent other than a C1 to C10 alkyl group. Better luminance than the case can be obtained.

The compound represented by Formula 1 has three resonance structures, as shown in the following schematic, but in the present specification, only one resonance structure is used to represent the compound represented by Formula 1 above. That is, the compound represented by Formula 1 may be represented by any one of the three resonance structures.

[scheme]

The compound represented by Formula 1 may be represented by any one selected from the group consisting of compounds represented by Formula 1-1 to Formula 1-8 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

The length of the compound represented by Formula 1 may be 1 nm to 3 nm, for example 1.5 nm to 2 nm. When the compound represented by Formula 1 has a length within the above range, a core-shell dye having a structure of a core and a shell surrounding it may be formed. In other words, as the compound represented by Formula 1 has a length within the above range, the shell may be obtained in a structure surrounding the compound represented by Formula 1. In the case of using other compounds that do not fall within the length of the above range, it is difficult to expect improvement in durability due to difficulty in forming a structure in which the shell surrounds the core compound.

The compound represented by Formula 1 may have a maximum absorption peak at a wavelength of 530nm to 680nm. A photosensitive resin composition for a color filter having high luminance can be obtained by using the compound represented by Formula 1 having spectral characteristics as a dye, such as a green dye.

When the compound represented by Formula 1 is used in the photosensitive resin composition, the solubility in the solvent described below may be 5 or more, such as 5 to 10. The solubility can be obtained by the amount (g) of the dye (compound) dissolved in 100 g of the solvent. When the solubility of the compound represented by Formula 1 is within the above range, compatibility and coloring power with other components in the photosensitive resin composition, that is, a binder resin, a photopolymerizable monomer and a photopolymerization initiator described below, can be secured, and Precipitation can be prevented.

The compound represented by Formula 1 may have excellent heat resistance. That is, when measured with a thermogravimetric analyzer (TGA), the thermal decomposition temperature may be 200°C or higher, for example, 200°C to 300°C.

The shell surrounding the core including the compound represented by Formula 1 may be represented by Formula 4 or Formula 5.

[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,

L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group.

In Formulas 4 and 5, L ¹ to L ⁴ may each independently be a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is excellent, and the shell is easy to form a structure surrounding the core containing the compound represented by Chemical Formula 1.

For example, the core-shell dye according to an embodiment is a non-covalent bond, that is, a hydrogen bond, between an oxygen atom of the compound represented by Formula 1 and a hydrogen atom bonded with a nitrogen atom of the shell represented by Formula 4 or Formula 5. It may include.

The shell may be, for example, represented by the following Formula 4-1 or Formula 5-1.

[Formula 4-1]

[Chemical Formula 5-1]

The cage width of the shell may be 6.5 Å to 7.5 Å, and the volume of the shell may be 10 Å to 16 Å. Herein, the cage width refers to the distance inside the shell, such as the distance between two different phenylene groups, in which methylene groups are connected to both sides in the shell represented by Chemical Formula 4-1 or Chemical Formula 5-1. (See Fig. 1). When the shell has a cage width within the above range, a core-shell dye having a structure surrounding the core including the compound represented by Formula 1 can be obtained, and accordingly, the core-shell dye is added to the photosensitive resin composition. If so, it is possible to implement a color filter having excellent durability and high luminance.

The core-shell dye may include a core including the compound represented by Formula 1 and the shell in a molar ratio of 1:1. When present in the molar ratio, the shell, that is, the coating layer surrounding the core containing the compound represented by Formula 1 may be well formed.

For example, the core-shell dye may be represented by any one selected from the group consisting of compounds represented by Chemical Formulas 6 to 21, but is not limited thereto.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

The colorant may be used by mixing the green dye with a toning dye.

Examples of the toning dye include triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azaporphyrin dyes, indigo dyes, and xanthene dyes.

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

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. Nickel complex pigments, such as yellow pigment 150, etc. are mentioned. The pigments may be used alone or in combination of two or more, and are not limited to these examples.

As a solvent constituting the yellow pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like can be used, preferably propylene Glycol methyl ether acetate can be used.

The dispersant helps the pigment to be uniformly dispersed in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specifically, polyalkylene glycol or its ester, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid salt, alkyl amide alkylene oxide addition Water, alkyl amines, and the like may be used, and these may be used alone or in combination of two or more.

As the dispersion resin, an acrylic resin containing a carboxyl group may be used, which not only improves the stability of the pigment dispersion, but also improves the patternability of the pixel.

The dispersant constituting the yellow pigment dispersion may have an amine value of 30 mgKOH/g to 50 mgKOH/g, and the dispersion resin may have an acid value of 110 mgKOH/g to 130 mgKOH/g. have. In general, the dispersant constituting the yellow pigment dispersion has an amine value of about 100 mgKOH/g to about 120 mgKOH/g and an acid value of 100 mgKOH/g. When the amine value and the acid value of the dispersion resin are limited as above (limited to have an amine value lower than the amine value of the conventional dispersant and have an acid value higher than that of the conventional dispersion resin), compatibility with the above-described green dye is maximized, The brightness can be greatly improved. For example, as the yellow pigment dispersion, SF Yellow AF1169 manufactured by SANYO Corporation may be used. This is because the dispersant and dispersion resin constituting the SF Yellow AF1169 have an amine value of 40 mgKOH/g and an acid value of 120 mgKOH/g, respectively.

The core-shell green dye may be included in an amount less than that of the yellow pigment dispersion. For example, the green dye and the yellow pigment dispersion may be mixed and used in a weight ratio of 1:1.5 to 1:2. When mixed in the weight ratio range, high luminance may be maintained while maintaining color characteristics.

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

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

The kneading may be performed at a temperature of 40° C. to 100° C., and the filtration and washing may be performed by washing the inorganic salt with water and then filtering.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. 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, etc. 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.

The yellow pigment subjected to the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the yellow 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 3% to 15% by weight, such as 3% to 10% by weight, based on the total amount of the photosensitive resin composition. When the colorant is used within the above range, high luminance can be expressed in a desired color coordinate.

(A) Acrylic binder resin

The acrylic binder resin may include all structural units represented by Chemical Formulas 22 to 26 below.

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

In Chemical Formulas 22 to 26,

R ¹¹ and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ¹² is a substituted or unsubstituted C1 to C10 alkyl group,

R ¹⁷ is a substituted or unsubstituted C11 to C20 alkyl group,

L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group.

As the photosensitive resin composition according to an embodiment includes an acrylic binder resin including all structural units represented by Chemical Formulas 22 to 26, heat resistance is enhanced to improve brightness, and furthermore, surface wrinkles can be controlled. So that the luminance can be further improved.

With respect to the total amount of the acrylic binder resin, the structural unit represented by Formula 22 is included in 20% to 30% by weight, the structural unit represented by Formula 23 is included in 15% to 25% by weight, and the formula The structural unit represented by 24 is included in 5% to 10% by weight, the structural unit represented by Chemical Formula 25 is included in 30% to 45% by weight, and the structural unit represented by Formula 26 is 5% by weight It may be included in to 15% by weight.

Particularly, when the structural unit represented by Chemical Formula 23 is included in an amount of less than 15% by weight or more than 25% by weight with respect to the total amount of the acrylic binder resin, surface properties are deteriorated, and there is a limit to improvement in brightness.

The acrylic binder resin may be included in an amount of 1% to 7% by weight, for example, 1% to 5% by weight based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included within the above range, luminance, heat resistance, and developability are excellent in manufacturing a color filter, and crosslinking properties are improved, thereby obtaining excellent surface smoothness.

In addition, the acrylic binder resin may have a double bond equivalent of 500g/eq to 350g/eq. If the double bond equivalent of the acrylic binder resin has a value lower than 500 g/eq (e.g., 600 g/eq, etc.), the number of double bonds in the acrylic binder resin is too large, so that polymerization does not occur, and the double bond equivalent of the acrylic binder resin If the value is higher than 350 g/eq (eg, 300 g/eq, etc.), the number of double bonds required for crosslinking may be insufficient, and crosslinking property may be deteriorated.

The acrylic binder resin may have a weight average molecular weight of 2,000 g/mol to 9,000 g/mol, and an acid value of 100 mgKOH/g to 120 mgKOH/g. When the acrylic binder resin has a weight average molecular weight and acid value in the above range, developability and adhesion of the formed pattern are excellent when implementing a pattern.

The photosensitive resin composition may further include (A') an epoxy-based binder resin. The epoxy-based binder resin may secure dispersion stability of the above-described dyes and pigments, and at the same time help to form pixels having a desired resolution during development.

The photosensitive resin composition according to the embodiment may further include an epoxy binder resin, thereby improving heat resistance. The epoxy binder resin may include, for example, 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.

For example, the epoxy-based binder resin may include a compound represented by Formula 27 below. For example, the epoxy-based binder resin may be represented by Formula 27 below.

[Formula 27]

The epoxy equivalent weight of the epoxy-based binder resin may be 200 g/eq to 150 g/eq. When using an epoxy-based binder resin having an epoxy equivalent within the above range, there is an advantageous effect in improving the curing degree of the formed pattern and fixing the dye within the structure in which the pattern is formed.

The acrylic binder resin may be included in an amount higher than that of the epoxy binder resin.

The epoxy-based binder resin may be included in an amount of 0.1% to 5% by weight, for example, 0.1% to 3% by weight based on the total amount of the photosensitive resin composition.

(C) Photopolymerization Monomer

The photopolymerizable monomer may be represented by Chemical Formula 2.

In general, the photosensitive resin composition for a curly filter uses dipentaerythritol hexaacrylate alone as a photopolymerizable monomer, but this photosensitive resin composition is applied on a substrate, exposed, developed, and cured (postbaked). When the photosensitive resin film is manufactured, water stains occur on the pattern of the photosensitive resin film, which is a cause of impeding improvement in luminance.

However, the photosensitive resin composition according to an embodiment may reliably solve the water stain problem by including the compound represented by Formula 2 as a photopolymerizable monomer, and thus improve brightness. Further, the compound represented by Formula 2 is easily adjusted to cure, and when used together with the above-described acrylic binder resin and colorant, brightness can be maximized.

The photopolymerizable monomer represented by Formula 2 may be used after treatment with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 2% to 8% by weight, for example, 3% to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included within the above range, hardening occurs sufficiently during exposure in the pattern formation process, resulting in excellent reliability, and excellent developability in an alkali developer.

(D) Light polymerization Initiator

The photoinitiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and the like.

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

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

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

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

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

The photopolymerization initiator may be used together with a photosensitizer that absorbs light and becomes excited, and then transmits the energy to cause a chemical reaction.

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

The photopolymerization initiator may be included in an amount of 1% to 3% by weight, such as 1% to 2% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization occurs sufficiently during exposure in the pattern formation process, and a decrease in transmittance due to an unreacted initiator may be prevented.

(E) solvent

The solvent may be materials that have compatibility with the binder resin, the colorant, the photopolymerizable monomer, and the photopolymerization initiator, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl 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-butylkenone, methyl-n-amyl ketone, and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate, and butyl hydroxyacetate; Acetic acid alkoxyalkyl esters such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, and ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acenyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, There are ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more.

In consideration of miscibility and reactivity in the solvent, preferably ketones such as cyclohexanone; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycols 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 a balance, such as 60% to 90% by weight, such as 70% to 90% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, a coating film having excellent applicability and flatness of the photosensitive resin composition can be obtained.

(F) other additives

The photosensitive resin composition may include malonic acid in order to prevent spots or spots during application, to improve leveling performance, and to prevent generation of residues due to undeveloped images; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; Radical polymerization initiator; Or it may further include other additives such as a combination thereof.

Examples of the silane-based coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, γ -Glycidoxy propyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like, and these may be used alone or in combination of two or more.

Examples of the fluorine-based surfactant, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^{® of} Dai Nippon Inki Chemical High School Co., Ltd.; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to desired physical properties.

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

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

The manufacturing method of the color filter is as follows.

A resin composition layer is formed by applying the above-described photosensitive resin composition to a thickness of, for example, 0.5 µm to 10 µm using a suitable method such as spin coating, roller coating, and spray coating on the glass substrate.

Subsequently, light is irradiated on the substrate on which the resin composition layer is formed to form a pattern required for a color filter. As a light source used for irradiation, UV, electron beam, or X-ray may be used, and for example, UV in a region of 190 nm to 450 nm, specifically 200 nm to 400 nm may be irradiated. In the irradiation step, a photoresist mask may be further used. After performing the step of irradiating in this way, the resin composition layer irradiated with the light source is treated with a developer. At this time, the non-exposed portion of the resin composition layer is dissolved to form a pattern necessary for the color filter. By repeating this process according to the number of required colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above process is heated again or cured by irradiation with actinic rays, crack resistance, solvent resistance, and the like can be improved.

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.

(Manufacture of acrylic binder resin)

Synthesis example A to Synthesis example F

After adding 2 g of AIBN as an initiator to a 100 ml beaker, the polymerization monomers specified in Table 1 below were sequentially added in a ratio of weight% specified in Table 1 so that the sum of the polymerization monomers became 40 g, and stirred for 30 minutes. Thereafter, in order to proceed with the polymerization reaction, 70 g of PGMEA was added to a 250 ml glass reactor equipped with a cooler, and then the temperature was raised to 85° C., and the prepared monomer solution was added dropwise to the reactor for 3 hours. After the reaction was further performed at the same temperature for 6 hours, the temperature was lowered to room temperature and the reaction was terminated, and the reaction was carried out under a nitrogen atmosphere.

(Unit: wt%) Monomer for polymerization Synthesis Example A Synthesis Example B Synthesis Example C Synthesis Example D Synthesis Example E Synthesis Example F Methacrylic acid 30 20 30 20 30 25 Isobonyl acrylate 20 20 20 20 10 30 N-Phenyl maleimide 10 5 10 10 10 5 Glycidyl methacrylate 30 45 30 45 40 30 Lauryl acrylate 10 10 10 5 10 10 Weight average molecular weight
(Mw, g/mol) 8,500 11,000 13,000 11,000 12,000 9,000 Double bond equivalent
(g/eq) 500 460 500 450 450 480

(Core-shell dye manufacturing)

( Synthesis example 1: Synthesis of Intermediate A-1)

Aniline (10 mol), 4-bromotoluene (10 mol), Pd ₂ (dba) ₃ (0.1 mol), and Xphos (0.1 mol) were added to toluene, heated to 100° C., and stirred for 24 hours. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain Intermediate A-1.

( Synthesis example 2: Synthesis of Intermediate A-2)

It was synthesized in the same manner as in Synthesis Example 1, except that bromo mesitylene was used instead of 4-bromotoluene, to obtain Intermediate A-2.

( Synthesis example 3: Synthesis of Intermediate B-1)

Intermediate A-1, bromo-2-ethylhexane, and sodium hydride were added to N,N-dimethylformamide, heated to 80° C., and stirred for 24 hours. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain Intermediate B-1.

( Synthesis example 4: Synthesis of Intermediate B-2)

Intermediate B-2 was obtained by synthesizing in the same manner as in Synthesis Example 3, except that intermediate A-2 was used instead of intermediate A-1.

( Synthesis example 5: Synthesis of Intermediate C-1)

2,4-dimethyldiphenylamine (10 mol), 1-bromo-2-methylpropane (10 mol) and sodium hydride (10 mol) were added to N,N-dimethylformamide and heated to 80℃ for 24 hours. While stirring. Ethyl acetate was added to this solution, washed twice with water, and the organic layer was extracted. The extracted organic layer was distilled under reduced pressure and separated by column chromatography to obtain Intermediate C-1.

( Synthesis example 6: Synthesis of Intermediate C-2)

Intermediate C-2 was obtained by synthesizing in the same manner as in Synthesis Example 5, except that 1-bromo-3-methylbutane was used instead of 1-bromo-2-methylpropane.

( Synthesis example 7: Synthesis of Intermediate C-3)

Intermediate C-3 was obtained by synthesizing in the same manner as in Synthesis Example 5, except that 1-bromo-4-methylpentane was used instead of 1-bromo-2-methylpropane.

( Synthesis example 8: synthesis of intermediate C-4)

Intermediate C-4 was obtained by synthesis in the same manner as in Synthesis Example 5, except that 1-bromo-2-ethylhexane was used instead of 1-bromo-2-methylpropane.

( Synthesis example 9: Synthesis of Intermediate C-5)

Synthesis was performed in the same manner as in Synthesis Example 5, except that 1-bromo-3,7-dimethyloctane was used instead of 1-bromo-2-methylpropane to obtain Intermediate C-5.

( Synthesis example 10: synthesis of intermediate C-6)

Intermediate C-6 was obtained by synthesizing in the same manner as in Synthesis Example 5, except that (bromomethyl)cyclohexane was used instead of 1-bromo-2-methylpropane.

( Synthesis example 11: Synthesis of a compound represented by Formula 1-1)

Intermediate B-1 (60 mmol), 3,4-dihydroxy-3-cyclobutine-1,2-dione (30 mmol) was added to toluene (200 mL) and butanol (200 mL) and refluxed. The water is removed with a Dean-stark distillation unit. After stirring for 12 hours, the green reactant was distilled under reduced pressure and purified by column chromatography to obtain a compound represented by Formula 1-1.

( Synthesis example 12: Synthesis of a compound represented by Formula 1-2)

Synthesis was performed in the same manner as in Synthesis Example 11, except that intermediate B-2 was used instead of intermediate B-1 to obtain a compound represented by Formula 1-2.

( Synthesis example 13: Formula 1- To 3 Synthesis of the displayed compound)

Synthesis was carried out in the same manner as in Synthesis Example 11, except that intermediate C-1 was used instead of intermediate B-1 to obtain a compound represented by Formula 1-3.

( Synthesis example 14: Synthesis of a compound represented by Formula 1-4)

Synthesis was performed in the same manner as in Synthesis Example 11, except that intermediate C-2 was used instead of intermediate B-1 to obtain a compound represented by Chemical Formula 1-4.

( Synthesis example 15: Synthesis of a compound represented by Formula 1-5)

Synthesis was performed in the same manner as in Synthesis Example 11, except that intermediate C-3 was used instead of intermediate B-1 to obtain a compound represented by Formula 1-5.

( Synthesis example 16: Synthesis of a compound represented by Formula 1-6)

Synthesis was carried out in the same manner as in Synthesis Example 11, except that intermediate C-4 was used instead of intermediate B-1 to obtain a compound represented by Formula 1-6.

( Synthesis example 17: Synthesis of a compound represented by Formula 1-7)

Synthesis was performed in the same manner as in Synthesis Example 11, except that intermediate C-5 was used instead of intermediate B-1 to obtain a compound represented by Chemical Formula 1-7.

( Synthesis example 18: Synthesis of a compound represented by Formula 1-8)

Synthesis was performed in the same manner as in Synthesis Example 11, except that intermediate C-6 was used instead of intermediate B-1 to obtain a compound represented by Formula 1-8.

( Synthesis example 19: chemical formula To 6 Synthesis of indicated core-shell dyes)

After dissolving the compound represented by Formula 1-1 (5 mmol) in 600 mL of chloroform solvent, isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform and added dropwise at room temperature for 5 hours. After 12 hours, distillation under reduced pressure and separation by column chromatography to obtain a compound represented by Formula 6 (Maldi-tof MS: 1200.65 m/z).

( Synthesis example 20: Synthesis of core-shell dye represented by Chemical Formula 7)

After dissolving the compound represented by Formula 1-1 (5 mmol) in 600 mL chloroform solvent, triethylamine (50 mmol) is added. 2,6-pyridinedicarbonyl dichloride (20 mmol) and p-xylylenediamine (20 mmol) were dissolved in 60 mL of chloroform and added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and separated by column chromatography to obtain a compound represented by Chemical Formula 7 (Maldi-tof MS: 1203.64 m/z).

( Synthesis example 21: Synthesis of core-shell dye represented by Chemical Formula 8)

A compound represented by Formula 8 (Maldi-tof MS: 1256.71 m/z) was synthesized in the same manner as in Synthesis Example 19, except that the compound represented by Formula 1-2 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 22: Synthesis of core-shell dye represented by Chemical Formula 9)

A compound represented by Formula 9 was obtained by synthesizing in the same manner as in Synthesis Example 20 except that the compound represented by Formula 1-2 was used instead of the compound represented by Formula 1-1.

Maldi-tof MS: 1258.70 m/z

( Synthesis example 23: Synthesis of core-shell dye represented by Chemical Formula 10)

A compound represented by Formula 10 (Maldi-tof MS: 1116.56 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-3 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 24: Synthesis of core-shell dye represented by Chemical Formula 11)

A compound represented by Formula 11 (Maldi-tof MS: 1118.54 m/z) was synthesized in the same manner as Synthesis Example 20, except that the compound represented by Formula 1-3 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 25: Synthesis of core-shell dye represented by Chemical Formula 12)

A compound represented by Formula 12 (Maldi-tof MS: 1144.58 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-4 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 26: Synthesis of core-shell dye represented by Chemical Formula 13)

A compound represented by Formula 13 (Maldi-tof MS: 1146.57 m/z) was synthesized in the same manner as Synthesis Example 20, except that the compound represented by Formula 1-4 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 27: Synthesis of core-shell dye represented by Chemical Formula 14)

A compound represented by Formula 14 (Maldi-tof MS: 1172.61 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-5 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 28: Synthesis of core-shell dye represented by Chemical Formula 15)

A compound represented by Formula 15 (Maldi-tof MS: 1174.60 m/z) was synthesized by the same method as Synthesis Example 20, except that the compound represented by Formula 1-5 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 29: Synthesis of core-shell dye represented by Chemical Formula 16)

A compound represented by Formula 16 (Maldi-tof MS: 1228.68 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 30: Synthesis of core-shell dye represented by Chemical Formula 17)

A compound represented by Formula 17 (Maldi-tof MS: 1230.67 m/z) was synthesized in the same manner as Synthesis Example 20, except that the compound represented by Formula 1-6 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 31: Synthesis of core-shell dye represented by Chemical Formula 18)

A compound represented by Formula 18 (Maldi-tof MS: 1284.74 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 32: Synthesis of core-shell dye represented by Chemical Formula 19)

A compound represented by Formula 19 (Maldi-tof MS: 1286.73 m/z) was synthesized in the same manner as in Synthesis Example 20, except that the compound represented by Formula 1-7 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 33: Synthesis of core-shell dye represented by Chemical Formula 20)

A compound represented by Formula 20 (Maldi-tof MS: 1196.61 m/z) was synthesized in the same manner as Synthesis Example 19, except that the compound represented by Formula 1-8 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 34: Synthesis of core-shell dye represented by Chemical Formula 21)

A compound represented by Formula 21 (Maldi-tof MS: 1198.60 m/z) was synthesized in the same manner as Synthesis Example 20, except that the compound represented by Formula 1-8 was used instead of the compound represented by Formula 1-1. Obtained.

( Synthesis example 35: synthesis of core-shell dye)

After adding 398 mg of squaric acid and 2.23 g of 2-(3-(dibutylamino)phenoxy)ethyl acrylate to a 100 mL 3-neck flask, 40 mL of n-butanol and 20 mL of toluene were added, followed by heating at 120° C. for 5 hours to reflux. I did. Water generated during the reaction was removed and the reaction was accelerated by using a Dean-Stark trap set. After the reaction was completed, the mixture was cooled, extracted with methylene chloride, and subjected to column chromatography to prepare a compound represented by the following formula (X) in a yield of 60%. Thereafter, 0.72g (1 mmol) of the compound represented by Formula X and triacetyl β-cyclodextrin (TCI, CAS# 23739-88-0) 2.02g (1 mmol) represented by Formula Y ) Was dissolved in 50 ml of dichloromethane, stirred at room temperature for about 12 hours, and then the solvent was completely removed and dried under reduced pressure to obtain about 2.7 g of a core-shell dye in a solid state. The core-shell dye was obtained in a structure in which the compound represented by Formula X is surrounded by the compound represented by Formula Y.

[Formula X]

[Formula Y]

(Production of photosensitive resin composition)

Example 1 to Example 8 and Comparative example 1 to Comparative example 3

The photosensitive resin compositions according to Examples 1 to 8 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 2 below using the components mentioned below.

Specifically, after accurately measuring the content of the photopolymerization initiator, a solvent was added and sufficiently stirred until the photopolymerization initiator was completely dissolved (30 minutes or more). Here, an acrylic binder resin, an epoxy binder resin, and a photopolymerizable monomer were sequentially added, followed by stirring for about 1 hour. Subsequently, after the colorant was added and other additives were added, the entire composition was finally stirred for at least 2 hours to prepare a photosensitive resin composition.

The specifications of each component used to prepare the photosensitive resin composition are as follows.

(A) Acrylic binder resin

(A-1) Acrylic binder resin of Synthesis Example A

(A-2) Acrylic binder resin of Synthesis Example B

(A-3) Acrylic binder resin of Synthesis Example C

(A-4) Acrylic binder resin of Synthesis Example D

(A-5) Acrylic binder resin of Synthesis Example E

(A-6) Acrylic binder resin of Synthesis Example F

(A') Epoxy binder resin

EHPE-3150 (DAICEL CHEMICAL) (Epoxy equivalent: 177g/eq)

(B) colorant

(B-1) Core-shell green dye prepared in Synthesis Example 30 (represented by Chemical Formula 17)

(B-2) Core-shell green dye prepared in Synthesis Example 35

(B-3) C.I. pigment green 36 (SANYO company)

(B-4) SF Yellow AF1169 (SANYO company)

(B-5) C.I. pigment yellow 138 (SANYO company)

(C) Photopolymerization Monomer

(C-1) KAYARAD DPCA-60 (Japan Explosives Corporation)

(C-2) KAYARAD DPCA-30 (Japan Explosives Corporation)

(C-3) KAYARAD DPCA-120 (Japan Explosives Corporation)

(C-4) KAYARAD DPHA (Japan Explosives Corporation)

(D) Light polymerization Initiator

Oxime initiator (SPI-03, Samyang Corporation)

(E) solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) other additives

Fluorine-based surfactant (F-554 (10% diluted solution used), DIC)

(Unit: wt%) Kinds Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Acrylic binder resin A-1 1.74 - - - - - 1.74 1.74 1.74 1.74 1.74 A-2 - 1.74 - - - - - - - - - A-3 - - 1.74 - - - - - - - - A-4 - - - 1.74 - - - - - - - A-5 - - - - 1.74 - - - - - - A-6 - - - - - 1.74 - - - - - (A') Epoxy binder resin 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 0.74 (B) colorant B-1 1.92 1.92 1.92 1.92 1.92 1.92 1.92 1.92 1.92 - - B-2 - - - - - - - - - 1.92 - B-3 - - - - - - - - - - 1.92 B-4 3.35 3.35 3.35 3.35 3.35 3.35 3.35 - 3.35 3.35 3.35 B-5 - - - - - - - 3.35 - - - (C) photopolymerizable monomer C-1 3.53 3.53 3.53 - 3.53 3.53 - 3.53 - 3.53 3.53 C-2 - - - 3.53 - - - - - - - C-3 - - - - - - 3.53 - - - - C-4 - - - - - - - - 3.53 - - (D) photopolymerization initiator 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47 (E) solvent 87.22 87.22 87.22 87.22 87.22 87.22 87.22 87.22 87.22 87.22 87.22 (F) other additives 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Total 100 100 100 100 100 100 100 100 100 100 100

Evaluation 1: Color characteristics evaluation

After coating at an rpm capable of exhibiting a predetermined thickness for each of the photosensitive resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 using a coating machine (Mikasa, Opticoat MS-A150), 90 Pre-baking was carried out on a hot-plate. Thereafter, the front exposure was performed in an exposure machine (Ushio, HB-50110AA) under the exposure condition of 50mj/cm ² , and baking was performed at 230° C. for 20 minutes in an oven condition, thereby completing the specimen production. Before and after baking the oven, the color characteristics were measured using the MCPD 3000 equipment, and the results are shown in Table 3 below.

Gx Gy Luminance (Y) Example 1 Bake I 0.2762 0.5696 64.80 After Bake 0.2774 0.5703 65.39 Example 2 Bake I 0.2760 0.5697 64.68 After Bake 0.2772 0.5704 65.16 Example 3 Bake I 0.2761 0.5697 64.73 After Bake 0.2774 0.5704 65.01 Example 4 Bake I 0.2752 0.5698 64.68 After Bake 0.2762 0.5705 64.91 Example 5 Bake I 0.2744 0.5714 64.51 After Bake 0.2752 0.5721 64.75 Example 6 Bake I 0.2756 0.5694 64.38 After Bake 0.2763 0.5703 64.68 Example 7 Bake I 0.2762 0.5697 64.77 After Bake 0.2765 0.5705 64.69 Example 8 Bake I 0.2767 0.5697 64.71 After Bake 0.2764 0.5705 63.56 Comparative Example 1 Bake I 0.2767 0.5697 64.71 After Bake 0.2766 0.5706 63.34 Comparative Example 2 Bake I 0.2469 0.5698 64.35 After Bake 0.2471 0.5674 63.21 Comparative Example 3 Bake I 0.2473 0.5688 64.24 After Bake 0.2477 0.5692 63.11

From Table 3, in the case of the photosensitive resin compositions of Examples 1 to 8, compared to the photosensitive resin compositions of Comparative Examples 1 to 3, it can be seen that color characteristics such as luminance are greatly excellent. This is because the structure of the green dye was modified and a photopolymerizable monomer optimized for the modified green dye was used. Furthermore, it can be confirmed that the luminance can be further improved by limiting the amine value and the acid value of the dispersant and the dispersion resin constituting the yellow pigment dispersion. In addition, it can be seen that the content of the monomer including the structural unit represented by Formula 23 among the monomers constituting the acrylic binder resin plays an important role in improving luminance.

The present invention is not limited to the above embodiments, but may be manufactured in a variety of different forms, and a person of ordinary skill in the art to which the present invention pertains to other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that it can be implemented with. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

Claims (23)

(A) acrylic binder resin;
(B) a colorant comprising a green dye and a yellow pigment dispersion;
(C) a photopolymerizable monomer represented by the following formula (2);
(D) photopolymerization initiator;
(E) solvent; And
Epoxy-based binder resin having an epoxy equivalent of 200 g/eq to 150 g/eq
Including,
The green dye is a photosensitive resin composition comprising a core including a compound represented by the following Formula 1 and a shell surrounding the core:
[Formula 1]

In Formula 1,
R ¹ to R ⁴ are each independently a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
[Formula 2]

In Chemical Formula 2,
R ⁵ to R ¹⁰ are each independently represented by the following formula (3),
[Formula 3]

In Chemical Formula 3,
n is an integer of 0 to 2.
The method of claim 1,
The R ¹ and R ³ are each independently a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ² and R ⁴ are each independently a C1 to C10 alkyl group or a C3 to C10 A photosensitive resin composition which is a C6 to C20 aryl group substituted with a cycloalkyl group.
The method of claim 1,
The compound represented by Formula 1 is a photosensitive resin composition represented by any one selected from the group consisting of compounds represented by Formulas 1-1 to 1-8.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

The method of claim 1,
The shell is a photosensitive resin composition represented by the following Chemical Formula 4 or Chemical Formula 5.
[Formula 4]

[Formula 5]

(In Chemical Formula 4 and Chemical Formula 5,
L ¹ to L ⁴ are each independently a single bond or a substituted or unsubstituted C1 to C10 alkylene group)
The method of claim 4,
The L ¹ to L ⁴ are each independently a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 4,
The shell is a photosensitive resin composition represented by the following Formula 4-1 or Formula 5-1.
[Formula 4-1]

[Chemical Formula 5-1]

The method of claim 6,
The shell is a photosensitive resin composition having a cage width of 6.5Å to 7.5Å.
The method of claim 1,
The length of the core is 1nm to 3nm photosensitive resin composition.
The method of claim 1,
The core photosensitive resin composition having a maximum absorption peak at a wavelength of 530nm to 680nm.
The method of claim 1,
The core-shell dye is a photosensitive resin composition represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas 6 to 21.
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

The method of claim 1,
The core-shell dye is a photosensitive resin composition comprising the core and the shell in a molar ratio of 1:1.
The method of claim 1,
The yellow pigment dispersion comprises a yellow pigment, a dispersant and a dispersion resin, the dispersant has an amine value of 30 mgKOH/g to 50 mgKOH/g, and the dispersion resin is 110 mgKOH/g to 130 mgKOH/g Photosensitive resin composition having an acid value (acid value).
The method of claim 1,
The acrylic binder resin is a photosensitive resin composition including all structural units represented by the following Chemical Formulas 22 to 26:
[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

In Chemical Formulas 22 to 26,
R ¹¹ and R ¹³ to R ¹⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ¹² is a substituted or unsubstituted C1 to C10 alkyl group,
R ¹⁷ is a substituted or unsubstituted C11 to C20 alkyl group,
L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 13,
With respect to the total amount of the acrylic binder resin,
The structural unit represented by Formula 22 is included in an amount of 20% to 30% by weight,
The structural unit represented by Formula 23 is included in 15% to 25% by weight,
The structural unit represented by Formula 24 is included in 5% to 10% by weight,
The structural unit represented by Formula 25 is included in 30% to 45% by weight,
The structural unit represented by Formula 26 is included in 5% to 15% by weight.
Photosensitive resin composition to become.
The method of claim 1,
The acrylic binder resin is a photosensitive resin composition having a double bond equivalent of 500g / eq to 350g / eq.
delete The method of claim 1,
The epoxy-based binder resin is a photosensitive resin composition comprising a compound represented by the following formula (27).
[Formula 27]

delete The method of claim 1,
The photosensitive resin composition contained in the acrylic binder resin in an amount higher than that of the epoxy binder resin.
The method of claim 1,
The photosensitive resin composition
(A) 1% to 7% by weight of the acrylic binder resin;
3% to 15% by weight of the colorant (B);
(C) 2% to 8% by weight of the photopolymerizable monomer;
(D) 1% to 3% by weight of the photopolymerization initiator;
70% to 90% by weight of the solvent (E); And
0.1% to 5% by weight of the epoxy-based binder resin
Photosensitive resin composition comprising a.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane-based coupling agents; Leveling agents; Fluorine-based surfactant; Radical polymerization initiator; Or a photosensitive resin composition further comprising an additive of a combination thereof.
A photosensitive resin film manufactured using the photosensitive resin composition of any one of claims 1 to 15, 17 and 19 to 21.
A color filter comprising the photosensitive resin film of claim 22.

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