KR20190063974A - Photosensitive resin composition and photosensitive resin layer using the same and color filter - Google Patents

Abstract

The present invention relates to a photosensitive resin composition capable of securing high brightness characteristics, and to a color filter manufactured using the same. The photosensitive resin composition comprises: (A) an acrylic binder resin; (B) a colorant including a green dye and a yellow pigment dispersion; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; and (E) a solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a photosensitive resin film produced using the same, and a color filter comprising the photosensitive resin film.

Recently, as the spread of the large-screen liquid crystal display device has expanded, a demand for a new performance enhancement for the liquid crystal display device has been increasing. Among the components of the liquid crystal display device, the color filter is the most important color realizing device. Research is continuing.

In addition, in the case of a large-screen liquid crystal display device, the colorant concentration of the photosensitive resin composition is increased in manufacturing a color filter in order to increase the color purity. In order to increase productivity and yield in the production process, a photosensitive resin composition having a low developing speed and excellent sensitivity .

The color filter using the photosensitive resin composition can be produced by coating three or more kinds of hues on a transparent substrate mainly by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method and the like. 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 limit in that the luminance and the contrast ratio are lowered due to the pigment particle size and the aggregation of the pigment particles. In order to overcome such limitations, attempts have been made to use a dye-type photosensitive resin composition which does not form particles or has a dye having a very small primary particle diameter relative to the pigment dispersion. However, the dye-type photosensitive resin composition is difficult to commercialize due to its weak heat resistance, light resistance and chemical resistance.

One embodiment is to provide a photosensitive resin composition capable of ensuring high brightness characteristics.

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

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

One 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) a photopolymerization initiator; And (E) a solvent, wherein the green dye is a photosensitive resin composition comprising a core comprising a compound represented by the following formula (1) and a shell surrounding the core:

[Chemical 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,

(2)

In Formula 2,

R ⁵ to R ¹⁰ each independently represent the following formula (3)

(3)

In Formula 3,

n is an integer of 0 to 2;

Wherein R ¹ and R ³ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group or a substituted or unsubstituted C 3 to C 20 cycloalkyl group and R ² and R ⁴ are each independently a C 1 to C 10 alkyl group or a C 3 to C 10 Or 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 Chemical Formulas 1-1 to 1-8.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

The cell may be represented by the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas (4) and (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 independently be a substituted or unsubstituted C1 to C10 alkylene group.

The cell may be represented by the following formula (4-1) or (5-1).

[Formula 4-1]

[Formula 5-1]

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

The length of the core may be between 1 nm and 3 nm.

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

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

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

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

Wherein the dispersing agent has an amine value of 30 mgKOH / g to 50 mgKOH / g, and the dispersed resin has a hydroxyl value of 110 mgKOH / g to 130 mgKOH / g Of acid value.

The acrylic binder resin may include all the structural units represented by the following formulas (22) to (26).

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

In the above 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 C 1 to C 10 alkyl group,

R ¹⁷ is a substituted or unsubstituted C 11 to C 20 alkyl group,

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

The structural unit represented by the formula (22) is contained in an amount of 20 to 30% by weight, the structural unit represented by the formula (23) is contained in an amount of 15 to 25% by weight based on the total amount of the acrylic binder resin, 24 is contained in an amount of 5 to 10% by weight, the structural unit represented by the formula (25) is contained in an amount of 30 to 45% by weight, the structural unit represented by the formula (26) By weight to 15% by weight.

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

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

The epoxy-based binder resin may include a compound represented by the following formula (27).

(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 contained in an amount larger than that of the epoxy-based binder resin.

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

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof.

Another embodiment provides a photosensitive resin film produced using the photosensitive resin composition.

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

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

The photosensitive resin composition according to one embodiment ensures color reproducibility, exposure sensitivity and fine pattern in manufacturing a color filter pattern while using the conventional process as it is, has excellent heat resistance, and can significantly increase luminance characteristics in particular.

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

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Means that at least one hydrogen atom of the functional group of the present invention is substituted with a halogen atom (F, Cl, Br or I), a hydroxyl 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, each independently being a C1 to C10 alkyl groups), amidino group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alicyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And a substituted or unsubstituted heterocyclic group substituted with at least one substituent selected from the group consisting of a substituted or unsubstituted heterocyclic group.

Unless otherwise specified in the specification, "alkyl group" means C1 to C20 alkyl group, specifically C1 to C15 alkyl group, "cycloalkyl group" means C3 to C20 cycloalkyl group, specifically C3 Refers to a C1 to C20 alkoxy group, specifically, a C1 to C18 alkoxy group, and an "aryl group" means a C6 to C20 aryl group, specifically, a C6 to C20 aryl group, Refers to a C 2 to C 20 alkenyl group, specifically, a C 2 to C 18 alkenyl group, and the "alkylene group" refers to a C 1 to C 20 alkylene group, specifically, a C1 Refers to a C6 to C20 arylene group, and specifically refers to a C6 to C16 arylene group.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition according to one embodiment comprises (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) a photopolymerization initiator; And (E) a solvent. The green dye comprises a core comprising a compound represented by the following formula (1) and a shell surrounding the core.

[Chemical 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,

(2)

In Formula 2,

R ⁵ to R ¹⁰ each independently represent the following formula (3)

(3)

In Formula 3,

n is an integer of 0 to 2;

The improvement in general luminance proceeded in the direction of improvement of the green pigment and the yellow pigment, but the improvement of the luminance was limited only by the simple pigment improvement. However, according to one embodiment, the green dye can be improved and used with a photopolymerizable monomer that affects the degree of curing, thereby maximizing the luminance improvement effect. The photopolymerizable monomer used in the photosensitive resin composition according to one embodiment is represented by the above formula (2), which can control the degree of curing unlike the conventionally used dipentaerythritol hexaacrylate (DPHA) and the like. When used in combination with a green dye, it can contribute to maximizing luminance.

Each component will be described in detail below.

(B) Colorant

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

The green dye has a core-shell structure, and the core may include a compound represented by the formula (1). Specifically, the shell can form a coating layer while surrounding the compound represented by the formula (1).

The compound represented by the above formula (1) is a compound having excellent green spectral characteristics and a high molar extinction coefficient, and is suitable for use as a green dye. However, since the durability of the pigment is poor, the luminance may be lowered in the baking process after the color resist is manufactured. In one embodiment, the shell corresponding to the macrocyclic compound surrounds the compound represented by Formula 1, that is, the structure in which the compound represented by Formula 1 exists in the macrocycle forming the shell The durability can be improved, and thus a color filter of high luminance can be realized.

Wherein R ¹ and R ³ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group or a substituted or unsubstituted C 3 to C 20 cycloalkyl group, and R ² and R ⁴ are each independently a C 1 to C 10 alkyl group Or 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 C 6 to C 20 aryl group substituted with a C ¹ to C 10 alkyl group, R ² and / or R ⁴ is a C 6 to C 20 aryl group substituted with a substituent other than a C ¹ to C 10 alkyl group It is possible to obtain an excellent luminance.

The compound represented by the formula (1) has three resonance structures as shown in the following diagram, but for the sake of convenience, the compound represented by the formula (1) is merely represented by one resonance structure. 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 Chemical Formulas 1-1 to 1-8.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical 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 the core may be formed. In other words, as the compound represented by the formula (1) has a length within the above range, the shell can be obtained with a structure surrounding the compound represented by the formula (1). It is difficult to expect improvement in durability because it is difficult to form a structure surrounding the compound which is a core of the shell when another compound which does not correspond to the length of the above range is used.

The compound represented by Formula 1 may have a maximum absorption peak at a wavelength of 530 nm to 680 nm. By using the compound represented by the general formula (1) having the spectroscopic characteristics as a dye, for example, a green dye, a photosensitive resin composition for a color filter having a high luminance can be obtained.

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

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

The shell surrounding the core containing the compound represented by the formula (1) may be represented by the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)

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

In the general formulas (4) and (5), L ¹ to L ⁴ each independently represent a substituted or unsubstituted C1 to C10 alkylene group. In this case, the solubility is excellent, and the shell tends to form a structure surrounding the core containing the compound represented by the above formula (1).

For example, the core-shell dye according to one embodiment is a non-covalent bond between the oxygen atom of the compound represented by Formula 1 and the hydrogen atom bonded to the nitrogen atom of the shell represented by Formula 4 or Formula 5, . ≪ / RTI >

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

[Formula 4-1]

[Formula 5-1]

The cage width of the shell may be 6.5 ANGSTROM to 7.5 ANGSTROM, and the volume of the shell may be 10 ANGSTROM to 16 ANGSTROM. Herein, the cage width means a distance between two different phenylene groups in which a methylene group is connected on both sides of the shell, for example, in the shell represented by the above formula (4-1) or (5-1) (See Fig. 1). When the shell has a cage width within the above range, it is possible to obtain a core-shell dye having a structure which surrounds the core containing the compound represented by the formula (1), and thus the core-shell dye is added to the photosensitive resin composition A color filter having excellent durability and high brightness can be realized.

The core-shell dye may include a core containing the compound represented by Formula 1 and the shell in a molar ratio of 1: 1. When present at the above-mentioned molar ratio, the shell, i.e., the coating layer surrounding the core including the compound represented by the formula (1) may well be formed.

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

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

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

Examples of the coloring dye include triarylmethane dyes, anthraquinone dyes, benzylidene dyes, cyanine dyes, phthalocyanine dyes, azapphyrin 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 comprise a solvent.

Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. And yellow complex pigments such as yellow pigment 150 and the like. These pigments can be used singly or in combination of two or more thereof, but are not limited to these examples.

As the 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. Among them, propylene Glycol methyl ether acetate can be used.

The dispersant helps to uniformly disperse the pigment in the dispersion, and any nonionic, anionic or cationic dispersant may be used. Specific examples thereof include polyalkylene glycols or esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts Water, alkylamine, and the like. These may be used alone or in combination of two or more.

The dispersion resin may use an acrylic resin containing a carboxyl group, which not only improves the stability of the pigment dispersion but also improves the patterning of pixels.

The dispersant constituting the yellow pigment dispersion has 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. Generally, the dispersing agent 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. The dispersant constituting the yellow pigment dispersion When the acid value of the amine value and the dispersion resin is limited as described above (which has an amine value lower than the amine value of the conventional dispersant and is limited so as to have an acid value higher than the acid value of the conventional dispersion resin), compatibility with the above-mentioned green dye is maximized, The luminance can be greatly improved. For example, as the yellow pigment dispersion, SF Yellow AF1169 manufactured by SANYO corporation may be used. The dispersant and dispersing resin constituting the SF Yellow AF1169 each 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 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, it is possible to maintain a high luminance while maintaining color characteristics.

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

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

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

The yellow pigment after 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 with excellent heat resistance and light resistance.

The colorant may be included in an amount of 3% by weight to 15% by weight, for example, 3% by weight 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 exhibited in a desired color coordinate.

(A) Acrylic binder resin

The acrylic binder resin may include all the structural units represented by the following formulas (22) to (26).

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

In the above 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 C 1 to C 10 alkyl group,

R ¹⁷ is a substituted or unsubstituted C 11 to C 20 alkyl group,

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

Since the photosensitive resin composition according to one embodiment includes the acrylic binder resin including all of the structural units represented by the above formulas (22) to (26), the heat resistance can be enhanced and the brightness can be improved. Further, So that the luminance can be further improved.

The structural unit represented by the formula (22) is contained in an amount of 20 to 30% by weight, the structural unit represented by the formula (23) is contained in an amount of 15 to 25% by weight based on the total amount of the acrylic binder resin, 24 is contained in an amount of 5 to 10% by weight, the structural unit represented by the formula (25) is contained in an amount of 30 to 45% by weight, the structural unit represented by the formula (26) By weight to 15% by weight.

Particularly, when the structural unit represented by the formula (23) is contained in an amount of less than 15% by weight or more than 25% by weight based on the total amount of the acrylic binder resin, surface characteristics are lowered and brightness improvement is limited.

The acrylic binder resin may be contained in an amount of 1 wt% to 7 wt%, for example, 1 wt% to 5 wt% with respect to the total amount of the photosensitive resin composition. When the acrylic binder resin is contained within the above range, excellent brightness, heat resistance and developability are obtained in the production of a color filter, and crosslinkability is improved and excellent surface smoothness can be obtained.

The acrylic binder resin may have a double bond equivalent of 500 g / eq to 350 g / eq. If the double bond equivalent of the acrylic binder resin has a value lower than 500 g / eq (for example, 600 g / eq or the like), the number of double bonds in the acrylic binder resin becomes too large and the polymerization reaction does not take place. Has a value higher than 350 g / eq (for example, 300 g / eq or the like), the number of double bonds necessary for crosslinking may be insufficient and the crosslinkability may be lowered.

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 an acid value in the above range, the developability and the adhesion of the pattern formed are excellent when the pattern is realized.

The photosensitive resin composition may further comprise (A ') an epoxy-based binder resin. The epoxy-based binder resin can ensure dispersion stability of the above-mentioned dyes and pigments, and can also help to form pixels of a desired resolution in the development process.

The heat-resistant property of the photosensitive resin composition according to one embodiment can be improved by further including an epoxy binder resin. Examples of the epoxy binder resin include phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, alicyclic epoxy resin, and combinations thereof. It is not.

For example, the epoxy-based binder resin may include a compound represented by the following formula (27). For example, the epoxy-based binder resin may be represented by the following chemical formula (27).

(27)

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

The acrylic binder resin may be contained in an amount larger than that of the epoxy-based binder resin.

The epoxy-based binder resin may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the photosensitive resin composition.

(C) Photopolymerization  Monomer

The photopolymerizable monomer may be represented by the general formula (2).

In general, a photosensitive resin composition for a culler filter uses dipentaerythritol hexaacrylate alone as a photopolymerizable monomer. However, such a photosensitive resin composition is coated on a substrate, exposed, developed and cured (post baking) In the case of producing a photosensitive resin film, water stains occur in the pattern of the photosensitive resin film, which causes the improvement of the luminance.

However, the photosensitive resin composition according to one embodiment can reliably solve the water stain problem by including the compound represented by the general formula (2) as a photopolymerizable monomer, thereby improving the brightness. Further, the compound represented by the above formula (2) can easily control the degree of curing, and when used together with the above-mentioned acrylic binder resin and colorant, the brightness can be maximized.

The photopolymerizable monomer represented by the general formula (2) may be treated with an acid anhydride so as to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 2% by weight to 8% by weight, for example, 3% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in reliability, and is excellent in developability in an alkaline developer.

(D) Light curing Initiator

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

Examples of the acetophenone compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

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

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

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

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a nonimidazole compound, or a fluorene compound in addition to the above compounds.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include 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 1 wt% to 3 wt%, for example, 1 wt% to 2 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(E) Solvent

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

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl 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 methylethylcarbitol, diethylcarbitol, 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- ; 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 methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl 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-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

Considering the miscibility and reactivity of the solvent, ketones such as cyclohexanone are preferred; Glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in a residual amount, for example, from 60% by weight to 90% by weight, such as from 70% by weight to 90% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, a coating film excellent in coating property of the photosensitive resin composition and excellent in flatness can be obtained.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof, and the like.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly 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 ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; 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 properties.

Another embodiment provides a photosensitive resin film produced using the above-described photosensitive resin composition.

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

A method of manufacturing the color filter is as follows.

The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.

Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV of 190 nm to 450 nm, specifically 200 nm to 400 nm, can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, 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 a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

(Preparation of acrylic binder resin)

Synthetic example  A to Synthetic example  F

After adding 2 g of AIBN as a initiator to a 100 ml beaker, the polymerization monomers listed in Table 1 were added in the ratio shown in Table 1 so that the sum of the polymerization monomers was 40 g, and the mixture was stirred for 30 minutes. Thereafter, 70 g of PGMEA was charged into a 250 ml glass reactor equipped with a condenser, and the temperature of the system was elevated to 85 캜. The prepared monomer solution was added dropwise to the reactor for 3 hours. After further reaction at the same temperature for 6 hours, the temperature was lowered to room temperature and the reaction was terminated. The reaction was carried out under a nitrogen atmosphere.

(Unit: wt%) The 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 preparation)

( Synthetic 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 placed in toluene and heated to 100 ° C and stirred for 24 hours. Ethyl acetate was added to this solution and the mixture was washed twice with water to extract an organic layer. The extracted organic layer was distilled under reduced pressure and purified by column chromatography to obtain Intermediate A-1.

( Synthetic example  2: Synthesis of intermediate A-2)

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

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

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

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

Intermediate B-2 was obtained in the same manner as in Synthesis Example 3 except for using Intermediate A-2 instead of Intermediate A-1.

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

(10 mol), 1-bromo-2-methylpropane (10 mol) and sodium hydride (10 mol) were placed in N, N-dimethylformamide, Lt; / RTI > Ethyl acetate was added to this solution and the mixture was washed twice with water to extract an organic layer. The extracted organic layer was subjected to vacuum distillation and separated by column chromatography to obtain Intermediate C-1.

( Synthetic example  6: Synthesis of intermediate C-2)

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

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

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

( Synthetic example  8: Synthesis of Intermediate C-4)

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

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

Synthesis was conducted 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.

( Synthetic example  10: Synthesis of Intermediate C-6)

Synthesis was conducted in the same manner as in Synthesis Example 5 except that (bromomethyl) cyclohexane was used in place of 1-bromo-2-methylpropane to obtain Intermediate C-6.

( Synthetic example  11: Synthesis of Compound Represented by Formula 1-1)

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

( Synthetic example  12: Synthesis of Compound Represented by Formula 1-2)

Synthesis was conducted 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.

( Synthetic example  13: 1- To 3  Synthesis of the indicated compound)

Synthesis was conducted in the same manner as in Synthesis Example 11 except that Intermediate C-1 was used instead of Intermediate B-1 to obtain the compound represented by Formula 1-3.

( Synthetic example  14: Synthesis of Compound Represented by Formula 1-4)

Synthesis was conducted 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 Formula 1-4.

( Synthetic example  15: Synthesis of Compound Represented by Formula 1-5)

Synthesis was conducted 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 the formula (1-5).

( Synthetic example  16: Synthesis of Compound Represented by Formula 1-6)

Synthesis was conducted in the same manner as in Synthesis Example 11 except that Intermediate C-4 was used instead of Intermediate B-1 to obtain the compound represented by Formula 1-6.

( Synthetic example  17: Synthesis of Compound Represented by Formula 1-7)

Synthesis was conducted 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 the general formula 1-7.

( Synthetic example  18: Synthesis of a compound represented by the general formula 1-8)

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

( Synthetic example  19: To 6  Synthesis of the indicated core-shell dye)

The compound (5 mmol) represented by formula (1-1) is dissolved in 600 mL of chloroform, and isophthaloyl chloride (20 mmol) and p-xylylenediamine (20 mmol) are dissolved in 60 mL of chloroform and then simultaneously added dropwise at room temperature for 5 hours. After 12 hours, the mixture was distilled under reduced pressure and the residue was purified by column chromatography to obtain a compound represented by the formula (6) (Maldi-tof MS: 1200.65 m / z).

( Synthetic example  20: Synthesis of core-shell dye represented by formula (7)

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

( Synthetic example  21: Synthesis of core-shell dye 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 .

( Synthetic example  22: Synthesis of core-shell dye represented by formula (9)

Was synthesized 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) to obtain a compound represented by Formula (9).

Mald-tof MS: 1258.70 m / z

( Synthetic example  23: Synthesis of core-shell dye represented by formula (10)

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

( Synthetic example  24: Synthesis of core-shell dye represented by formula (11)

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

( Synthetic example  25: Synthesis of core-shell dye represented by formula (12)

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

( Synthetic example  26: Synthesis of core-shell dye represented by formula (13)

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

( Synthetic example  27: Synthesis of core-shell dye represented by formula (14)

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

( Synthetic example  28: Synthesis of core-shell dye represented by formula (15)

(Maldi-tof MS: 1174.60 m / z) was synthesized in the same manner as in Synthesis Example 20, except that the compound represented by Formula (1-5) was used in place of the compound represented by Formula .

( Synthetic example  29: Synthesis of core-shell dye represented by formula (16)

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

( Synthetic example  30: Synthesis of core-shell dye represented by formula (17)

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

( Synthetic example  31: Synthesis of core-shell dye represented by formula (18)

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

( Synthetic example  32: Synthesis of core-shell dye 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 .

( Synthetic example  33: Synthesis of core-shell dye represented by formula (20)

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

( Synthetic example  34: Synthesis of core-shell dye represented by formula (21)

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

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

398 mg of squalic acid and 2.23 g of 2- (3- (dibutylamino) phenoxy) ethyl acrylate were placed in a 100 mL three-necked flask, and 40 mL of n-butanol and 20 mL of toluene were added. Respectively. Dean-Stark trap set was used to remove the water generated during the reaction and promote the reaction. After completion of the reaction, the reaction mixture was cooled, extracted with methylene chloride, and then subjected to column chromatography to obtain a compound represented by the following formula (X) in a yield of 60%. Thereafter, 0.72 g (1 mmol) of the compound represented by the above formula (X) and 2.02 g (1 mmol) of triacetyl beta-cyclodextrin (TCI, CAS # 23739-88-0) ) Was dissolved in 50 ml of dichloromethane. After stirring for about 12 hours at room temperature, 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 the formula (X) was surrounded by the compound represented by the formula (X).

(X)

[Formula Y]

(Preparation 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 the following Table 2 by using the following components.

Specifically, the content of the photopolymerization initiator was precisely measured, the solvent was then added, and the mixture was sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was sufficiently dissolved. To this, an acrylic binder resin, an epoxy binder resin and a photopolymerizable monomer were sequentially added, followed by stirring for about 1 hour. Then, a colorant was added, other additives were added, and the entire composition was finally stirred for 2 hours or more to prepare a photosensitive resin composition.

The specifications of each component used in the production of the photosensitive resin composition are as follows.

(A) Acrylic binder resin

(A-1) The acrylic binder resin of Synthesis Example A

(A-2) The acrylic binder resin of Synthesis Example B

(A-3) The acrylic binder resin of Synthesis Example C

(A-4) The acrylic binder resin of Synthesis Example D

(A-5) The acrylic binder resin of Synthesis Example E

(A-6) The acrylic binder resin of Synthesis Example F

(A ') Epoxy-based binder resin

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

(B) Colorant

(B-1) The core-shell green dye (represented by Formula 17) prepared in Synthesis Example 30,

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

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

(B-4) SF Yellow AF1169 (SANYO)

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

(C) Photopolymerization  Monomer

(C-1) KAYARAD DPCA-60 (Nippon Kayaku Co., Ltd.)

(C-2) KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd.)

(C-3) KAYARAD DPCA-120 (Nippon Kayaku Co., Ltd.)

(C-4) KAYARAD DPHA (Nippon Kayaku)

(D) Light curing Initiator

Oxime initiator (SPI-03, Samyang)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) Other additives

Fluorine-based surfactant (F-554 (using 10% diluent), 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-based 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) a 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) a 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

Rating 1: Color characteristics  evaluation

Coating was carried out at rpm at which a certain thickness could be exhibited for each of the photosensitive resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 by using a coating machine (Mikasa, Opticoat MS-A150) Pre-baking was carried out on a hot-plate. Thereafter, the entire surface was exposed using an exposure machine (Ushio, HB-50110AA) under an exposure condition of 50 mj / cm ² , and baking was performed at 230 캜 for 20 minutes in an oven condition to complete the preparation of the test piece. Color characteristics were measured using an MCPD 3000 apparatus before and after the oven baking, 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

It can be seen from the above Table 3 that the photosensitive resin compositions of Examples 1 to 8 are significantly superior in color characteristics such as brightness as compared with the photosensitive resin compositions of Comparative Examples 1 to 3. This is because the structure of the green dye is modified and the photopolymerizable monomer optimized for the modified green dye is used. Furthermore, it can be confirmed that the luminance can be further improved by limiting the amine value and the acid value of the dispersing agent and dispersing resin constituting the yellow pigment dispersion. It can also be confirmed that the content of the monomer including the structural unit represented by the formula (23) plays an important role in improving the brightness in the monomers constituting the acrylic binder resin.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (23)

(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) a photopolymerization initiator; And
(E) Solvent
Lt; / RTI >
Wherein the green dye is a photosensitive resin composition comprising a core comprising a compound represented by the following Formula 1 and a shell surrounding the core:
[Chemical 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,
(2)

In Formula 2,
R ⁵ to R ¹⁰ each independently represent the following formula (3)
(3)

In Formula 3,
n is an integer of 0 to 2;
The method according to claim 1,
Wherein R ¹ and R ³ are each independently a substituted or unsubstituted C 1 to C 20 alkyl group or a substituted or unsubstituted C 3 to C 20 cycloalkyl group and R ² and R ⁴ are each independently a C 1 to C 10 alkyl group or a C 3 to C 10 A C6 to C20 aryl group substituted with a cycloalkyl group.
The method according to claim 1,
Wherein the compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-8.
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

The method according to claim 1,
Wherein the cell is represented by the following formula (4) or (5).
[Chemical Formula 4]

[Chemical Formula 5]

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

[Formula 5-1]

The method according to claim 6,
Wherein the cell has a cage width of 6.5 ANGSTROM to 7.5 ANGSTROM.
The method according to claim 1,
Wherein the core has a length of 1 nm to 3 nm.
The method according to claim 1,
Wherein the core has a maximum absorption peak at a wavelength of 530 to 680 nm.
The method according to claim 1,
Wherein the core-shell dye is represented by any one selected from the group consisting of compounds represented by the following Chemical Formulas (6) to (21).
[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

The method according to claim 1,
Wherein the core-shell dye comprises the core and the shell in a molar ratio of 1: 1.
The method according to claim 1,
Wherein the dispersing agent has an amine value of 30 mgKOH / g to 50 mgKOH / g, and the dispersed resin has a hydroxyl value of 110 mgKOH / g to 130 mgKOH / g Of an acid value of the photosensitive resin composition.
The method according to claim 1,
Wherein the acrylic binder resin comprises all of the structural units represented by the following Chemical Formulas 22 to 26:
[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

In the above 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 C 1 to C 10 alkyl group,
R ¹⁷ is a substituted or unsubstituted C 11 to C 20 alkyl group,
L ⁵ is a substituted or unsubstituted C1 to C10 alkylene group.
14. The method of claim 13,
With respect to the total amount of the acrylic binder resin,
The structural unit represented by the formula (22) is contained in an amount of 20% by weight to 30% by weight,
The structural unit represented by the formula (23) is contained in an amount of 15 to 25% by weight,
The structural unit represented by the formula (24) is contained in an amount of 5 to 10% by weight,
The structural unit represented by the formula (25) is contained in an amount of 30% by weight to 45% by weight,
The structural unit represented by the formula (26) is contained in an amount of 5 to 15% by weight
.
The method according to claim 1,
Wherein the acrylic binder resin has a double bond equivalent weight of 500 g / eq to 350 g / eq.
The method according to claim 1,
Wherein the photosensitive resin composition further comprises an epoxy-based binder resin.
17. The method of claim 16,
Wherein the epoxy-based binder resin comprises a compound represented by the following formula (27).
(27)

17. The method of claim 16,
Wherein the epoxy-based binder resin has an epoxy equivalent of 200 g / eq to 150 g / eq.
17. The method of claim 16,
Wherein the acrylic binder resin is contained in an amount larger than that of the epoxy-based binder resin.
The method according to claim 1,
The photosensitive resin composition
1 to 7% by weight of the acrylic binder resin (A);
3% to 15% by weight of (B) the colorant;
2% to 8% by weight of the (C) photopolymerizable monomer;
1 to 3% by weight of the photopolymerization initiator (D); And
60% to 90% by weight of the solvent (E)
.
The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof. ≪ / RTI >
A photosensitive resin film produced by using the photosensitive resin composition of any one of claims 1 to 21.
A color filter comprising the photosensitive resin film of claim 22.

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