TW201727368A - Photosensitive resin composition, photosensitive resin layer and color filter including the same - Google Patents

Abstract

Provided are a photosensitive resin composition including (A) a colorant including a dye polymer of a core-sell structure; (B) isocyanate-based thermal hardener; (C) a binder resin; (D) a photopolymerizable monomer; (E) a photopolymerization initiator; and (F) a solvent, wherein the dye polymer of the core-sell structure is a copolymer of a compound represented by Chemical Formula 1, a rhodamin-based compound, and an acrylic compound, and a photosensitive resin layer and a color filter using the same. [Chemical Formula 1] In Chemical Formula 1, each substituent is the same as defined in the detailed description.

Description

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

The present invention relates to a resin composition, and more particularly to a photosensitive resin composition, a photosensitive resin layer containing the same, and a color filter.

The color filter is used for a liquid crystal display (LCD), a filter for a camera, and the like. The color filter can be fabricated by coating a community of three or more colors of red, green, and blue on a charge coupled device or a transparent substrate. The color film can be produced by dyeing, printing, electrophoretic deposition (EPD), pigment dispersion method, or the like. Recently, a pigment dispersion method has been generally used.

The pigment dispersion method is a method of forming a color film by repeating a series of processes, for example, coating a photopolymerizable composition containing a colorant on a transparent substrate, exposure, development, and heat curing. The pigment dispersion method can improve heat resistance and durability, which are very important features of a color filter, and can provide a film having a uniform thickness. Therefore, the method is widely used.

However, when a color filter is manufactured using a pigment type photosensitive resin composition, the color filter has a limitation of deteriorated brightness and contrast due to the size and adhesion of the pigment particles. In order to improve these limitations, studies have been conducted on a photosensitive resin composition containing a dye which does not form particles and which does not have a very small initial particle diameter as compared with the pigment dispersion.

However, the dye-type photosensitive resin composition has poor heat resistance, light resistance, and chemical resistance, and is hardly available on the market. In addition, recent large-sized liquid crystal display devices require high brightness and high contrast characteristics, but pigment type photosensitive resin compositions may be difficult to meet these requirements.

Color filters are prepared by a number of chemical processes during the manufacturing process. In order to maintain the pattern formed under the above conditions, the color photosensitive resin needs to have a development boundary and chemical resistance, and thus improve the yield of the color filter. In other words, it is necessary to provide a photosensitive resin composition for a color filter having improved chemical resistance and chemical resistance to improve the yield of a color filter. Specifically, since the color filter of the liquid crystal display device is formed on the TFT array panel by a color filter-on-array (COA) method, a process of forming a transparent electrode on the color filter is required. The transparent conductive layer may be formed by sequentially forming a transparent conductive layer and a photosensitive resin layer on the color filter, exposing and developing and patterning the photosensitive resin layer, and using the patterned photosensitive resin layer. To make transparent electrodes. The color filter needs to have chemical resistance because the color filter may be exposed to different liquid chemicals such as a stripping solution for developing the photosensitive resin layer. In addition, the color filter needs to have heat resistance, and a plurality of heat treatments are required to form a color filter.

Therefore, research has been conducted on a photosensitive resin composition capable of producing a color filter having high luminance and improved heat resistance and chemical resistance.

One embodiment of the present invention provides a photosensitive resin composition having improved brightness, heat resistance and chemical resistance.

Another embodiment of the present invention provides a photosensitive resin layer produced using a photosensitive resin composition.

Another embodiment of the present invention provides a color filter including a photosensitive resin layer.

One embodiment of the present invention provides a photosensitive resin composition comprising (A) a colorant comprising a dye polymer having a core-shell structure; (B) an isocyanate type heat hardener; (C) a binder resin (D) photopolymerizable monomer; (E) photopolymerization initiator; and (F) solvent, wherein the dye polymer having a core-shell structure is a compound represented by Chemical Formula 1, rhodamin-based A copolymer of a compound and an acrylic compound. [Chemical Formula 1] In Chemical Formula 1, R ⁰ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and n is an integer in the range of 3 to 30.

The copolymer may contain 5 to 20% by weight of the compound represented by Chemical Formula 1, 20% by weight to 60% by weight of the rhodamine-based compound, and 30% by weight to 70% by weight of the acrylic compound, based on the total amount of the copolymer.

The rhodamine-based compound may include a functional group represented by Chemical Formula 2 at its terminal. [Chemical Formula 2] In Chemical Formula 2, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The rhodamine compound can be represented by Chemical Formula 3 or Chemical Formula 4. [Chemical Formula 3] [Chemical Formula 4] In Chemical Formula 3 and Chemical Formula 4, R ² to R ^{6 are} independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted. a C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, at least one of R ² to R ⁶ comprising a functional group represented by Chemical Formula 2, and X ⁻ from a chemical formula A to a chemical formula F Said. [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] PW ₁₂ O ₄₀ ^3- [Chemical Formula D] SiW ₁₂ O ₄₀ ^4- [Chemical Formula E] CF ₃ SO ₃ ^- [Chemical Formula F] ClO ₄ ^- .

The acrylic compound can be represented by Chemical Formula 5. [Chemical Formula 5] In Chemical Formula 5, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl or substituted or unsubstituted C6 to C20 aryl.

The acrylic compound may contain at least one compound selected from the compound represented by Chemical Formula 5-1, the compound represented by Chemical Formula 5-2, and the compound represented by Chemical Formula 5-3. [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] In Chemical Formula 5-1 to Chemical Formula 5-3, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, R ⁹ is a substituted or unsubstituted C3 to C20 cycloalkyl group, and R ¹⁰ is a substituted or unsubstituted C1 to C10 alkyl group.

The dye polymer can be a red dye polymer.

The isocyanate-based thermosetting agent may include a blocked isocyanate group represented by Chemical Formula 6 at its end. [Chemical Formula 6] In Chemical Formula 6, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryloxy group. A substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amine group.

R ¹¹ may be selected from Chemical Formula 6-1 to Chemical Formula 6-8. [Chemical Formula 6-1] In Chemical Formula 6-1, R ¹² is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group. [Chemical Formula 6-2] In Chemical Formula 6-2, R ¹³ to R ^{15 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. [Chemical Formula 6-3] In Chemical Formula 6-3, R ¹⁶ and R ^{17 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. [Chemical Formula 6-4] [Chemical Formula 6-5] In Chemical Formula 6-5, R ¹⁸ to R ^{21 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. [Chemical Formula 6-6] In Chemical Formula 6-6, R ²² and R ^{23 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. [Chemical Formula 6-7] In Chemical Formula 6-7, R ²⁴ and R ^{25 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. [Chemical Formula 6-8] In Chemical Formula 6-8, R ²⁶ and R ^{27 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

The isocyanate-based heat hardener can be represented by Chemical Formula 7 or Chemical Formula 8. [Chemical Formula 7] [Chemical Formula 8] In Chemical Formula 7 and Chemical Formula 8, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20. An aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amino group, R ²⁸ to R ^{31 are} independently a substituted or unsubstituted C1 to C10 alkyl group, L ¹ to L ^{12 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and m1 to m3 are independently in the range of 0 to 4 An integer inside.

The colorant may further comprise a metal complex dye and a pigment.

The amount of the dye polymer in the colorant may be from 0.1 to 5 times the total amount of the metal complex dye and the pigment in the color former.

The photosensitive resin composition may contain 10% by weight to 60% by weight of the colorant (A), 0.1% by weight to 5% by weight of the isocyanate type heat hardener (B), based on the total amount of the photosensitive resin composition; 1% by weight To 30% by weight of the binder resin (C); 1% by weight to 30% by weight of the photopolymerizable monomer (D); 0.1% by weight to 8% by weight of the photopolymerization initiator (E); and the remaining amount of the solvent (F) ).

The photosensitive resin composition may comprise at least one additive selected from the group consisting of malonic acid; 3-amino-1,2-propanediol; a coupling agent having a vinyl group or a (meth)acryloxy group; a leveling agent; a surfactant; and a radical polymerization initiator.

According to another embodiment, a photosensitive resin layer produced using a photosensitive resin composition is provided.

According to another embodiment, a color filter comprising a photosensitive resin layer is provided.

Other embodiments are included in the detailed description that follows.

The photosensitive resin composition according to one embodiment can realize a color filter having improved heat resistance and chemical resistance as well as high light-emitting characteristics.

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

In the present specification, the term "substituted" means that at least one hydrogen is replaced by at least one substituent selected from a halogen atom (F, Cl, Br or I), a hydroxyl group, C1 to when a specific definition is not additionally provided. C20 alkoxy, nitro, cyano, amine, imino, azido, indolyl, fluorenyl, fluorenylene, carbonyl, carbamyl, thiol, ester, ether, carboxyl Or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 Cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C30 heteroaryl or combinations thereof.

In the present specification, when a specific definition is not additionally provided, the term "alkyl" means a C1 to C30 alkyl group and specifically a C1 to C15 alkyl group, and the term "cycloalkyl group" means a C3 to C30 cycloalkyl group. And specifically C3 to C18 cycloalkyl, the term "alkoxy" refers to a C1 to C30 alkoxy group and specifically a C1 to C18 alkoxy group, and the term "aryl" refers to a C6 to C30 aryl group. And specifically C6 to C18 aryl, the term "alkenyl" refers to C2 to C30 alkenyl and specifically C2 to C18 alkenyl, and the term "alkylene" refers to C1 to C30 alkylene and specifically It is a C1 to C18 alkylene group, and the term "arylene" means a C6 to C20 arylene group and specifically a C6 to C16 arylene group.

In the present specification, a cycloalkyl group includes a bicycloalkyl group and a tricycloalkyl group.

In the present specification, the term "hetero" may mean that a ring substituent is substituted with at least one hetero atom of N, O, S and P instead of at least one C of the ring substituent, when a specific definition is not otherwise provided.

In the present specification, "(meth)acrylate" means "acrylate" and "methacrylate" when not specifically defined, and "(meth)acrylic" means "acrylic" and " Methacrylate".

In the present specification, the term "combination" means mixing or copolymerization when a specific definition is not otherwise provided.

In the present specification, unless a specific definition is additionally provided, when a chemical bond is not drawn, a hydrogen atom is bonded at a position given by the speculation.

In the present specification, a cardo-based resin refers to a resin including at least one functional group selected from Chemical Formulas 9-1 to 9-11 in the main chain.

In the present specification, when a specific definition is not additionally provided, "*" indicates a point connecting the same or different atoms or chemical formulas.

The photosensitive resin composition according to one embodiment comprises (A) a colorant comprising a dye polymer having a core-shell structure; (B) an isocyanate type heat hardener; (C) a binder resin; (D) light a polymerizable monomer; (E) a photopolymerization initiator; and (F) a solvent.

The dye polymer having a core-shell structure is a copolymer of a compound represented by Chemical Formula 1, a rhodamin-based compound, and an acrylic compound.

[Chemical Formula 1]

In Chemical Formula 1, R ⁰ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and n is an integer in the range of 3 to 30.

Since the dye-type photosensitive resin composition generally has high brightness and high contrast, but has deteriorated heat resistance and chemical resistance, attempts have been made to overcome the problem by including a dye having various structures, in fact, a dye-type photosensitive resin compound. The characteristics are not sufficient for the actual product. In addition, although the dye polymer has a core-shell structure, since the dye polymer does not directly participate in the curing reaction, it is difficult to ensure sufficient heat resistance and chemical resistance.

However, the photosensitive resin composition according to one embodiment comprises a dye polymer having a core-shell structure, wherein the dye polymer comprises a dye core composed of a rhodamine compound together with an acrylic compound and a shell layer of the compound represented by Chemical Formula 1. . Since the shell layer contains a reaction site which may cause a curing reaction with an isocyanate-based thermosetting agent, a carbamate thermosetting reaction may be induced during the patterning process, so that heat resistance and chemical resistance are improved. Further, the rhodamine-like compound is polymerized to form a core, that is, the dye polymer directly participates in the curing reaction, and thus has a great effect on improving heat resistance and chemical resistance.

Hereinafter, each component is described in detail.

( A )Colorant

The coloring agent of the photosensitive resin composition according to one embodiment is a dye polymer having a core-shell structure.

The dye polymer having a core-shell structure may be an acrylate-based core-shell dye polymer prepared by copolymerizing a rhodamine-based dye monomer and a compound represented by Chemical Formula 1 and an acrylic compound. That is, in the dye polymer, the rhodamine-based dye and the acrylic compound can form a core, and the compound represented by Chemical Formula 1 can form a shell layer as a reaction site.

When a rhodamine-based dye is copolymerized with the compound represented by Chemical Formula 1 and an acrylic compound, a carbamate thermosetting reaction with an isocyanate-based thermosetting agent (described later) may occur to ensure excellent heat resistance and chemical resistance. Sex. Further, the photocuring reaction proceeds together during the patterning process, and thus heat resistance and chemical resistance can be further improved.

The weight average molecular weight of the compound represented by Chemical Formula 1 may be from 230 g/mol to 2,000 g/mol, for example, from 300 g/mol to 2,000 g/mol. For example, in Chemical Formula 1, n may be an integer of 3 to 30, for example, 5 to 30, or 5 to 20.

When the weight average molecular weight of the compound represented by Chemical Formula 1 is less than 230 g/mol, for example, n in Chemical Formula 1 is an integer of less than 3, a shell layer is not formed and reactivity is rapidly deteriorated. When the weight average molecular weight of the compound represented by Chemical Formula 1 is more than 2,000 g/mol, for example, n in Chemical Formula 1 is an integer of more than 30, and developability and colorability are deteriorated.

For example, the copolymer of the dye polymer having a core-shell structure composed of the compound represented by Chemical Formula 1, the Rhodamine compound, and the acrylic compound may contain 5 wt% to 20 wt%, based on the total amount of the copolymer. (for example, 5% by weight to 15% by weight) of the compound represented by Chemical Formula 1, 20% by weight to 60% by weight (30% by weight to 50% by weight) of the rhodamine-based compound, and 30% by weight to 70% by weight (40% by weight to 60% by weight of an acrylic compound. When the compound represented by Chemical Formula 1, the Rhodamine-based compound, and the acrylic compound in the above range are contained in the copolymer, a dye polymer having a core-shell structure which ensures sufficient heat resistance and chemical resistance can be provided.

The dye polymer having a core-shell structure may have a weight average molecular weight of from 3,000 g/mol to 20,000 g/mol, such as from 5,000 g/mol to 15,000 g/mol. When the weight average molecular weight of the dye polymer having a core-shell structure is within the above range, excellent heat resistance and chemical resistance can be ensured.

The rhodamine-based compound may include a functional group represented by Chemical Formula 2 at its terminal.

[Chemical Formula 2]

In Chemical Formula 2, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

Since the rhodamine-based compound contains an acrylic functional group represented by Chemical Formula 2 at its terminal end, it reacts with an acrylic compound and polymerizes to provide a dye polymer. That is, as shown in FIG. 1, a rhodamine-like compound (monomer) provides a polymer core by reacting an acrylic monomer at its terminal with an acrylic compound; and the compound represented by Chemical Formula 1 forms a shell surrounding the core. .

For example, the rhodamine compound can be represented by Chemical Formula 3 or Chemical Formula 4.

[Chemical Formula 3]

[Chemical Formula 4]

In Chemical Formula 3 and Chemical Formula 4, R ² to R ^{6 are} independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted. a C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, at least one of R ² to R ⁶ comprising a functional group represented by Chemical Formula 2, and X ^{− is} represented by a chemical formula A to a chemical formula F .

[Chemical Formula A]

[Chemical Formula B]

[Chemical Formula C] PW ₁₂ O ₄₀ ^3-

[Chemical Formula D] SiW ₁₂ O ₄₀ ^4-

[Chemical Formula E] CF ₃ SO ₃ ^-

[Chemical Formula F] ClO ₄ ^-

For example, at least one of R ² to R ⁶ may be represented by, but not limited to, Chemical Formula 2-1.

[Chemical Formula 2-1]

In Chemical Formula 2-1, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L is a C1 to C10 alkylene group which is substituted or unsubstituted.

The acrylic compound can be represented by Chemical Formula 5.

[Chemical Formula 5]

In Chemical Formula 5, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl or substituted or unsubstituted C6 to C20 aryl.

For example, the acrylic compound may contain at least one compound selected from the compound represented by Chemical Formula 5-1, the compound represented by Chemical Formula 5-2, and the compound represented by Chemical Formula 5-3.

For example, the acrylic compound may include all compounds selected from the compound represented by Chemical Formula 5-1, the compound represented by Chemical Formula 5-2, and the compound represented by Chemical Formula 5-3.

[Chemical Formula 5-1]

[Chemical Formula 5-2]

[Chemical Formula 5-3]

In Chemical Formula 5-1 to Chemical Formula 5-3, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and R ⁹ is a substituted or unsubstituted C3 to C20 cycloalkyl group, R ¹⁰ It is a substituted or unsubstituted C1 to C10 alkyl group.

For example, R ⁹ may be substituted or unsubstituted C10 to C20 tricycloalkyl.

The dye polymer can be a red dye polymer. In this case, the rhodamine compound may be a rhodamine red dye.

On the other hand, the color former of the photosensitive resin composition according to one embodiment may be a metal complex dye and a pigment.

The amount of the dye polymer in the colorant may be from 0.1 to 5 times the total amount of the metal complex dye and the pigment in the color former. When the amount of the dye polymer, the metal complex dye, and the pigment is 0.1 to 5 times, for example, 0.1 to 3 times, relative to the total amount, the brightness can be improved.

The metal complex dye may be a compound exhibiting maximum absorbance in a wavelength region of 200 nm to 650 nm.

Specifically, the metal complex dye may be a yellow dye exhibiting maximum absorbance in a wavelength range of 200 nm to 400 nm, and an orange dye exhibiting maximum absorbance in a wavelength region of a wavelength region of 300 nm to 500 nm, at 500 nm to A red dye that exhibits maximum absorbance in the 650 nm wavelength region, or a combination thereof.

The metal complex dyes may be direct dyes, acid dyes, basic dyes, acid medium dyes, sulfur dyes, vat dyes, azo dyes, disperse dyes, reactive dyes, oxidation dyes, alcohol soluble dyes, azo dyes, Anthraquinone dye, indigo dye, cation dye, phthalocyanine dye, nitro dye, quinoline dye, cyanine dye, polymethicone dye or a combination thereof.

The metal complex may comprise at least one metal ion selected from the group consisting of Mg, Ni, Cu, Co, Zn, Cr, Pt, Pd, and Fe.

The metal complex dye may be a complex of at least one dye selected from the group consisting of Solvent Yellow 19, Solvent Yellow 21, Solvent Yellow 25, Solvent Yellow 79, Solvent Yellow 82, Solvent Yellow 88, Solvent Orange 45, Solvent Orange 54, Solvent orange 62, solvent orange 99, solvent red 8, solvent red 32, solvent red 109, solvent red 112, solvent red 119, solvent red 124, solvent red 160, solvent red 132 and solvent red 218, and metal ions.

The solubility of the metal complex dye for the solvent used in the photosensitive resin composition according to one embodiment (that is, the solvent (F) described below) may be greater than or equal to 5, for example, 5 to 10. Solubility refers to the amount of dye dissolved in 100 grams of solvent. When the solubility of the metal complex dye is within the above range, compatibility and coloring characteristics with other components of the photosensitive resin composition according to one embodiment can be ensured, and dye precipitation can be prevented.

The solvent may be, for example, propylene glycol monomethylether acetate (PGMEA), ethyl lactate (EL), ethylene glycol ethyl acetate (EGA), cyclohexanone, 3-methoxy-1-butanol or a combination thereof.

The amount of the metal complex dye may be from 0.1% by weight to 5% by weight, such as from 1% by weight to 5% by weight, based on the total amount of the photosensitive resin composition. When a metal complex dye within the range is used, high brightness and contrast can be exhibited in the desired color coordinates.

The pigment may in particular be a red pigment, a yellow pigment or an orange pigment, such as a red pigment.

The red pigment may specifically include a color index of CI Pigment Red 242, CI Pigment Red 214, CI Pigment Red 221, CI Pigment Red 166, CI Pigment Red 220, CI Pigment Red 248, CI Pigment Red 262, CI Pigment Red 254, CI Pigment Red 177 or the like, and they may be used singly or in the form of a mixture of two or more.

The pigment may further comprise at least one yellow pigment selected from C.I. yellow pigment 139, C.I. yellow pigment 138, and C.I. yellow pigment 150 to obtain a specified color characteristic.

The pigment can be prepared as a dispersion and contained in a photosensitive resin composition. Such pigment dispersions may contain pigments and solvents, dispersants, binder resins, and the like.

The solvent used in the pigment dispersion may be ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, 3 Methoxy-1-butanol, and specifically propylene glycol methyl ether acetate can be used.

The dispersant used in the pigment dispersion helps the pigment to be uniformly dispersed, and may contain a nonionic dispersant, an anionic dispersant or a cationic dispersant. Examples of the dispersant include polyalkylene glycol or an ester thereof, a polyoxyalkylene, a polyol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate, a sulfonate, a carboxylate, a carboxylate An alkylguanamine alkylene oxide addition product, an alkylamine, and they may be used singly or in the form of a mixture of two or more.

The binder resin used in the pigment dispersion may be an acrylic resin containing a carboxyl group, and the patterning property of the element and the stability of the pigment dispersion may be improved.

The pigment has an initial particle diameter in the range of 10 nanometers to 70 nanometers. When the initial particle diameter of the pigment is within the above range, the color has excellent stability in the dispersion and the resolution of the primitive can be improved.

The pigment does not have a specific limitation on the secondary particle diameter, but in consideration of the resolution of the primitive, the secondary particle diameter may be less than or equal to 200 nm, specifically 70 nm to 100 nm.

The pigment may be contained in an amount of from 20% by weight to 45% by weight, for example, from 30% by weight to 40% by weight, based on the total of the photosensitive resin composition. When the pigment in the range is used, high brightness can be displayed in the desired color coordinates.

The color former may be contained in an amount of 10% by weight to 60% by weight, for example, 20% by weight to 50% by weight based on the total amount of the photosensitive resin composition. When the coloring agent in the range is used, high brightness can be displayed in the desired color coordinates and a color filter having a thin color thickness can be manufactured.

( B ) Isocyanate Thermal Hardener

The isocyanate-based thermosetting agent may include a blocked isocyanate group represented by Chemical Formula 6 at its end.

[Chemical Formula 6]

In Chemical Formula 6, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryloxy group. A substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amine group.

The blocked isocyanate blocks the isocyanate so that the reaction between the isocyanate group and the hydroxyl group does not occur at room temperature. The hydroxyl groups in the urethane linkage generally exhibit a polyol that is reactive toward isocyanate. Since the block group dissociates near a predetermined temperature, the activated isocyanate reacts with the polyol to obtain a carbamate.

That is, since the block group does not dissociate during prebaking, the isocyanate-based thermosetting agent does not react with the dye polymer, and the block group is selectively dissociated only during post-baking and occurs with the dye polymer. Carbamate heat curing reaction.

Specifically, the isocyanate-based thermosetting agent is a reaction product of a compound containing an isocyanate group and a blocking agent. Since the isocyanate group is blocked by the blocking agent, the blocking agent dissociates at a temperature greater than or equal to the predetermined temperature, and the isocyanate group blocked by the blocking agent undergoes a carbamate thermosetting reaction with the hydroxyl group of the shell layer of the dye polymer, so that Heat resistance and chemical resistance are improved.

The temperature at which the blocking agent dissociates may vary depending on each blocking agent. Therefore, the isocyanate-based heat hardener can be prepared by selecting a blocking agent which can be dissociated at a desired temperature at which the isocyanate group is dissociated, and performing a carbamate thermosetting reaction of the isocyanate group, and reacting it with a compound containing an isocyanate group. For example, the blocking agent can be dissociated at a post-baking temperature of, for example, about 100 ° C to about 300 ° C, for example, about 120 ° C to about 250 ° C, or about 150 ° C to about 240 ° C, and the isocyanate-based heat hardener can It is prepared by using a blocking agent. The blocking agent may be, but not limited to, 3,5-dimethyl pyrazole (DMP), diethyl malonate (DEM), methyl ethyl ketone ( Methylethyl keoxime; MEKO), caprolactam (ε-CAP), triazole, diisopropylamine (DIPA), naphthol, and the like.

A method of preparing a blocked isocyanate group and a method of performing a carbamate reaction by dissociating a block group are shown in the following Reaction Scheme 1 and Reaction Scheme 2. Specifically, Reaction Scheme 1 illustrates a reaction scheme for blocking a reaction of an isocyanate group by a blocking agent; and Reaction Scheme 2 illustrates dissociation of a blocked isocyanate group at a predetermined temperature above room temperature to obtain a carbamate. The reaction process of the carbamate heat curing reaction.

[Reaction Scheme 1]

[Reaction Scheme 2]

R'-OH in Reaction Scheme 2 corresponds to a dye polymer having a core-shell structure. In the dye-polymer of a core-shell structure, the compound represented by Chemical Formula 1 forms a shell layer, and a plurality of hydroxyl groups are present in the shell layer.

For example, in Chemical Formula 6, R ¹¹ may be selected from, but not limited to, Chemical Formula 6-1 to Chemical Formula 6-8.

[Chemical Formula 6-1]

In Chemical Formula 6-1, R ¹² is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group.

[Chemical Formula 6-2]

In Chemical Formula 6-2, R ¹³ to R ^{15 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

[Chemical Formula 6-3]

In Chemical Formula 6-3, R ¹⁶ and R ^{17 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

[Chemical Formula 6-4]

[Chemical Formula 6-5]

In Chemical Formula 6-5, R ¹⁸ to R ^{21 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

[Chemical Formula 6-6]

In Chemical Formula 6-6, R ²² and R ^{23 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

[Chemical Formula 6-7]

In Chemical Formula 6-7, R ²⁴ and R ^{25 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

[Chemical Formula 6-8]

In Chemical Formula 6-8, R ²⁶ and R ^{27 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group.

For example, the isocyanate-based heat hardener can be represented by Chemical Formula 7 or Chemical Formula 8.

[Chemical Formula 7]

[Chemical Formula 8]

In Chemical Formula 7 and Chemical Formula 8, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20. An aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amino group, R ²⁸ to R ^{31 are} independently a substituted or unsubstituted C1 to C10 alkyl group, L ¹ to L ^{12 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and m1 to m3 are independently in the range of 0 to 4 The integer.

When the isocyanate-based thermosetting agent is a compound represented by Chemical Formula 7 or Chemical Formula 8, the blocking agent is dissociated at a temperature of 100 ° C or more in both cases, and thus the blocking agent is not dissociated at the time of prebaking and UV curing It is carried out at a temperature of less than or equal to 100 ° C and thus does not react with the dye polymer. In this case, although the CD uniformity characteristic and the BP time are not affected, at the same time, no reaction occurs between the isocyanate-based heat hardener and the dye polymer, so that no residue remains during development.

Further, the blocking agent of the isocyanate-based thermosetting agent is only dissociated at the time of post-baking, and reacts with the hydroxyl group of the dye polymer, so that heat resistance and chemical resistance are improved.

The isocyanate-based heat hardener may be contained in an amount of 0.1% by weight to 5% by weight, for example, 0.1% by weight to 3% by weight, or 0.1% by weight to 1% by weight based on the total amount of the photosensitive resin composition. When the isocyanate-based thermosetting agent in the range is included, heat resistance, chemical resistance, and storage stability are improved and the pattern size can be made uniform.

( C ) Binder resin

The photosensitive resin composition according to one embodiment contains a binder resin, and the binder resin may contain a cardanoid binder resin, an acrylic binder resin, or a combination thereof.

The ruthenium-based binder resin can be represented by Chemical Formula 9.

[Chemical Formula 9]

In Chemical Formula 9, R ⁵¹ and R ^{52 are} independently a hydrogen atom or a substituted or unsubstituted (meth) acryloxyalkyl group, and R ⁵³ and R ^{54 are} independently a hydrogen atom, a halogen atom or a substituted Or unsubstituted C1 to C20 alkyl, Z ¹ is a single bond, O, CO, SO ₂ , CR ⁵⁵ R ⁵⁶ , SiR ⁵⁷ R ⁵⁸ (wherein R ⁵⁵ to R ^{58 are} independently hydrogen atoms, or substituted or An unsubstituted C1 to C20 alkyl group or one of the linking groups represented by Chemical Formula 9-1 to Chemical Formula 9-11.

[Chemical Formula 9-1]

[Chemical Formula 9-2]

[Chemical Formula 9-3]

[Chemical Formula 9-4]

[Chemical Formula 9-5]

In Chemical Formula 9-5, R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH=CH ₂ or a phenyl group.

[Chemical Formula 9-6]

[Chemical Formula 9-7]

[Chemical Formula 9-8]

[Chemical Formula 9-9]

[Chemical Formula 9-10]

[Chemical Formula 9-11]

Z ² is an acid dianhydride residue, and n1 and n2 are independently an integer ranging from 0 to 4.

The binder resin may have a weight average molecular weight of from 500 g/mol to 50,000 g/mol, for example from 1,000 g/mol to 30,000 g/mol. When the weight average molecular weight of the binder resin is within the range, a satisfactory residue-free pattern can be formed during the production of the light-blocking layer and without loss of film thickness during development.

The binder resin may contain a functional group represented by Chemical Formula 10 at at least one terminal.

[Chemical Formula 10]

In Chemical Formula 10, Z ^{3 is} represented by Chemical Formula 10-1 to Chemical Formula 10-7.

[Chemical Formula 10-1]

In Chemical Formula 10-1, R ^b and R ^{c are} independently hydrogen, substituted or unsubstituted C1 to C20 alkyl, ester or ether groups.

[Chemical Formula 10-2]

[Chemical Formula 10-3]

[Chemical Formula 10-4]

[Chemical Formula 10-5]

In Chemical Formula 10-5, R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamino group or a C2 to C20 allylamino group.

[Chemical Formula 10-6]

[Chemical Formula 10-7]

The binder resin can be prepared, for example, by mixing at least two of the following: a ruthenium-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)anthracene; an acid anhydride compound such as benzenetetrazide Formic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutane tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic acid a dianhydride and a tetrahydrophthalic anhydride; a diol compound such as ethylene glycol, propylene glycol, and polyethylene glycol; an alcohol compound such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; a solvent compound, For example, propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethyl chloride Base amine, triethylamine, tributylamine, benzyltriethylammonium chloride.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a repeating unit comprising at least one acrylic acid. Resin.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and examples of the monomer include (meth)acrylic acid, maleic acid, itaconic acid, fumaric acid Or a combination thereof.

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

The diene unsaturated monomer may contain an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylic acid ester compound such as (A) Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; aminoalkyl ester compound of unsaturated carboxylic acid, such as 2-aminoethyl (meth)acrylate, 2-(meth)acrylic acid Dimethylaminoethyl ester or the like; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth)acrylate; and the like; (Meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth) acrylamide or the like; and the like. It can be used singly or in the form of a mixture of two or more than two.

Specific examples of the acrylic resin may be, but not limited to, acrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/ Styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymerization Things and so on. It can be used singly or in the form of a mixture of two or more than two.

The acrylic binder resin may have a weight average molecular weight of from about 3,000 g/mol to 50,000 g/mol, such as from about 5,000 g/mol to 40,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the range, the close contact property and the physicochemical property with the substrate can be improved, and an appropriate viscosity can be provided.

The binder resin may be contained in an amount of from 1% by weight to 30% by weight, for example, from 1% by weight to 20% by weight based on the total of the photosensitive resin composition. When the binder resin within the range is included, improved sensitivity, developability, resolution, and pattern linearity can be obtained.

( D ) Photopolymerizable monomer

The photosensitive resin composition according to one embodiment contains a photopolymerizable monomer, and the photopolymerizable monomer may be a monofunctional ester or a polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

The photopolymerizable monomer has an ethylenically unsaturated double bond, and thus, sufficient polymerization can be caused during exposure during pattern formation, and a pattern having excellent heat resistance, light resistance, and chemical resistance is formed.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A (meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (methyl) Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol single Methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris(meth) propylene methoxyethyl phosphate, aldehyde epoxy (meth) acrylate, and the like.

Examples of commercially available reactive unsaturated compounds are as follows. Monofunctional (meth) acrylates may include Anix M-101 ^® (Aronix M-101 ^® ), M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.) )); Kayad TC-110S ^® (KAYARAD TC-110S ^® ), TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® ( Osaka Organic Chemical Ind., Ltd.). Examples of the difunctional (meth) acrylate may include Anix M-210 ^® , M-240 ^® , M-6200 ^® (East Asia Synthetic Chemical Co., Ltd.), Kayad HDDA ^® , HX-220 ^® , R-604 ^® (Nippon Kayaku Co., ^{Ltd.), V-260 ®, V} -312 ®, V-335 HP ® ( Osaka Organic Chemical industry Ltd.) and the like. Examples of trifunctional (meth) acrylates may include Anix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M-8060 ^® ( East Asia Synthetic Chemical Industry Co., Ltd., Kayad TPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Nippon Chemical Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Organic Chemical Industry Co., Ltd.), etc. These may be used singly or in the form of a mixture of two or more than two.

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

The photopolymerizable monomer may be contained in an amount of from 1% by weight to 30% by weight, for example from 1% by weight to 20% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer in the range is included, pattern characteristics and developability can be improved during the manufacture of the color filter.

( E Photopolymerization initiator

The photosensitive resin composition according to one embodiment contains a photopolymerization initiator. The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an anthraquinone compound or the like.

Examples of the acetophenone compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl group. Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (methylthio)phenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one Wait.

Examples of the benzophenone compound may be benzophenone, benzamidine benzoate, methyl benzhydrazide, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone. Ketone, 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 compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

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

Examples of the triazine compound may be 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(trichloro) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-double (trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s- Triazine, 2-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol 1-yl)-4,6-double (trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-syringyl-s-triazine, 2-4-bis(trichloromethyl)-6-(4 -Methoxystyryl)-s-triazine and the like.

An example of the quinone compound may be an O-indenyl hydrazine compound, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1 -(O-acetamidine)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, O-ethoxycarbonyl-α- Oxyamino-1-phenylpropan-1-one and the like. An example of the O-quinone compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-benzene -butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione 2-indole-O-benzoate, 1-(4-phenylthiobenzene -octane-1,2-dione 2-indole-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate, 1- (4-phenylthiophenyl)-butan-1-one oxime-O-acetate or the like.

The photopolymerization initiator may further contain a carbazole compound, a diketone compound, a lanthanum borate compound, a diazo compound, an imidazole compound, a biimidazole compound or the like in addition to the compound.

The photopolymerization initiator may be contained in an amount of 0.1% by weight to 8% by weight, and 0.1% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator in the range is contained, the composition may be sufficiently photopolymerized upon exposure during the pattern forming process for preparing a color filter, achieving excellent sensitivity and improving transmittance.

( F Solvent

The solvent is a material which is compatible with the dye polymer, the isocyanate-based thermosetting agent, the binder resin, the photopolymerizable monomer, and the photopolymerization initiator without reacting with them.

The solvent is not particularly limited, but examples of the solvent include alcohols such as methanol, ethanol, etc.; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, etc.; glycol ethers such as ethylene Alcohol methyl ether, ethylene glycol ether, propylene glycol methyl ether, etc.; cellosolve acetate, such as cellosolve methyl acetate, cellosolve ethyl acetate, cellosolve diethyl acetate, etc.; carbitol, A Ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol Ethyl ether, etc.; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone , 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl ester For example, ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; alkyl lactate, such as methyl lactate, ethyl lactate, etc.; alkyl glycolate, such as hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, etc.; alkoxyalkyl acetate, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxy acetate Methyl ester, ethoxyethyl acetate, etc.; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc.; alkyl 3-alkoxypropionate, for example Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-hydroxypropionate, For example, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, 2- Ethyl methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; alkyl 2-hydroxy-2-methylpropanoate, such as 2-hydroxy-2- Methyl methacrylate, ethyl 2-hydroxy-2-methylpropionate, etc.; alkyl 2-alkoxy-2-methylpropanoate, such as 2-methoxy-2-methylpropionic acid Methyl ester, ethyl 2-ethoxy-2-methylpropionate, etc.; esters, such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2- hydroxyl Methyl 3-methylbutyrate or the like; or a ketoester compound such as ethyl pyruvate. Further, the solvent may be N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide , N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetamidine, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzene acetate Methyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, cellosolve phenyl acetate, and the like. These may be used singly or in the form of a mixture of two or more than two.

The solvent may contain a glycol ether such as ethylene glycol monoethyl ether or the like in view of blending property, reactivity, etc.; ethylene glycol alkyl ether acetate such as cellosolve ethyl acetate; etc.; ester such as propionic acid 2 - hydroxyethyl ester or the like; diethylene glycol, such as diethylene glycol monomethyl ether; or propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

The balance contained is a solvent, and specifically, an amount of the solvent in an amount ranging from 30% by weight to 85% by weight based on the total amount of the photosensitive resin composition. When the solvent within the range is included, the photosensitive resin composition may have an appropriate viscosity and thus the coating processability can be improved.

( G Other additives

The photosensitive resin composition according to one embodiment may further contain other additives such as malonic acid; 3-amino-1,2-propanediol; a decane-based coupling agent containing a vinyl group or a (meth)acryloxy group; A flattening agent; a fluorine-based surfactant; and a radical polymerization initiator to prevent dyeing or speckle during coating, to adjust flatness or to prevent pattern residue generated by undeveloping.

Additives can be controlled according to the desired characteristics.

The coupling agent may be a decane type coupling agent, and examples of the decane type coupling agent may be trimethoxy decyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decyl decane. , vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane and so on. These may be used singly or in the form of a mixture of two or more than two.

The decane type coupling agent may be contained in an amount of from 0.01 part by weight to 1 part by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further contain a fluorine-based surfactant as needed.

Examples of the fluorine-based surfactant may include, but are not limited to, F-482, F-484, F-478, F-554, and the like manufactured by DIC Co., Ltd.

The fluorine-based surfactant may be contained in an amount of 0.01% by weight to 1% by weight, for example, 0.01% by weight to 0.8% by weight based on the total amount of the photosensitive resin composition. When the amount is outside the range, foreign particles after development may be generated.

The photosensitive resin composition according to one embodiment may be of an alkaline development type which can be cured by radiation light and developed with an alkaline aqueous solution. When a photosensitive resin composition is laminated on a substrate and a pattern for a color filter is formed by actinic radiation, the photosensitive resin composition is reacted by actinic rays, and thus, compared with the non-reactive region The solubility of the reaction zone is drastically reduced, and therefore, only the non-reaction zone can be selectively dissolved. In this way, the solution in which the non-exposed areas are removed is referred to as a developing solution, and this developing solution is classified into two types such as an organic solvent type and an alkaline developing type. Since the organic solvent type developing solution causes air pollution and causes damage to the human body, an alkaline developing type solution can be used as the environment. The photosensitive resin composition according to one embodiment uses an alkaline development type solution, and thus, can be effectively used in terms of the environment.

Another embodiment provides a color filter manufactured using the photosensitive resin composition. The thickness of the photosensitive resin layer may be from 1 micrometer to 5 micrometers, for example, from 2 micrometers to 4 micrometers.

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

This color filter can be produced by a general method, but specifically, a method of spin coating, roll coating, slit coating of a photosensitive resin composition on the glass, etc., so that the photosensitive resin composition has 1.0 micron to 5.0. Thickness in the micrometer range. After coating, ultraviolet (UV) ray radiation is used to form the desired pattern of the color filter, the coating layer is treated with an alkaline developing solution, and its unradiated area can be dissolved to form an image color filter. pattern. This process is repeated depending on the number of R, G, and B colors required to produce a color filter having a desired pattern. Further, the image pattern obtained by curing is cured by heat treatment, actinic radiation, or the like, thereby improving crack resistance, solvent resistance, and the like.

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

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are not to be construed as limiting the scope of the invention in any sense.

( Preparation of dye polymers )

Preparation example 1 To the preparation example 4 Preparation of comparative examples 1 And preparation of comparative examples 2

A dye polymer having a core-shell structure was prepared using the composition shown in Table 1 below. Specifically, 1.5 g of a photopolymerization initiator V601 (and WAKO Chemicals Inc.) was placed in a 100 ml beaker, and based on the total amount of 30 g of the acrylic monomer, as shown in Table 1 below. The rhodamine-based monomer and the acrylic compound were sequentially added in the weight percentages shown. 72 g of DAA (diacetone alcohol) was added thereto and stirred for 30 minutes until the rhodamine-based monomer, the acrylic compound, and the photopolymerization initiator were completely dissolved to obtain a solution. For the polymerization, 54 g of DAA was placed in a 250 ml 3-neck glass reactor equipped with a cooler and a nitrogen tube and heated to 85 ° C, and nitrogen bubbling was performed. Next, the obtained solution was added to the reactor in a dropwise manner for 3 hours, and reacted at the same temperature for 9 hours, and the temperature was lowered to room temperature to stop the reaction. The polymerization was carried out under a nitrogen atmosphere.

[Table 1] (Unit: % by weight)

Rhodamine monomer 1

(1) 50 g of 1 KRX-01 (catalog number 77545-45-0, Kyung-In Synthetic Corporation) was placed in a reactor and dissolved using 350 ml of isopropyl alcohol. 22.6 g of diethylamine was slowly added dropwise at a temperature not exceeding 20 ° C and stirred at 20 ° C for 3 hours. The reaction liquid was added to 2 liters of a 10% aqueous hydrochloric acid solution and precipitated. The obtained precipitate was suction filtered and further washed with pure water. The filtrate was dried to give 23.6 g (yield: 43%).

(2) Mixing the reactant 1 (7.5 g) obtained from (1) and 52.5 g of N-methylpyrrolidone at room temperature, and dropping 4.5 g of 2-(ethylamino) at a temperature not exceeding 20 °C. Ethanol and stirred at 60 ° C for 8 hours. The reaction liquid was cooled at room temperature and 263 g was added. The obtained precipitate was suction filtered and further washed with pure water. The filtrate was dried to give 23.6 g of Res. 2 (43% yield).

(3) Reactant 2 (5 g) obtained from (2) was placed in a reactor and dissolved using 35 ml of dichloromethane, followed by the addition of 1.4 ml of triethylamine and cooling at 0 °C. 1.2 g of methyl methacrylate was added dropwise to the cooled reaction mixture and heated at room temperature, and stirred at room temperature for 4 hours, followed by washing of the reaction liquid. The washed organic layer was distilled off under reduced pressure to remove an organic solvent. The obtained solid was dissolved with a small amount of dichloromethane, followed by dropwise addition to 100 ml of diethyl ether. The precipitate was suction filtered and further washed with diethyl ether, and the filtrate was finally dried to give 4.8 g of Rhodamine-type monomer 1 (84% yield).

Rhodamine monomer 2 ( Renjing Synthetic Co., Ltd. )

(Preparation of photosensitive resin composition)

Instance 1 To instance 5 And comparative examples 1 To the comparative example 2

The photopolymerization initiator was added to the solvent as shown in the composition as shown in Table 2, and stirred at room temperature for 1 hour to be dissolved in a solvent. Next, a binder resin and a photopolymerizable monomer were added, and the mixture was stirred at room temperature for 1 hour. Next, other additives were added and stirred at room temperature for 1 hour. The dye polymer, the pigment, and the metal complex dye prepared in Preparation Example 1 to Preparation Example 4 and Preparation Comparative Example 1 and Preparation Comparative Example 2 were added thereto, the mixture was stirred at room temperature for 2 hours, and the solution was filtered three times to Each of the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was prepared by removing impurities. The components used to prepare the photosensitive resin composition are as follows.

( A ) Colorant

Dye Polymer (A-1) According to Preparation of Dye Polymer (A-2) of Example 1 According to Preparation of Dye Polymer (A-3) of Preparation Example 2 According to Preparation of Dye Polymer (A-4) of Preparation Example 3 According to Preparation Example Dye Polymer (A-5) of 4 According to Preparation of Dye Polymer of Comparative Example 1 (A-6) According to Preparation of Dye Polymer of Comparative Example 2

Pigment CI Pigment Red 254 (Sanyo)

Metal Complex Dye Lily Baohong 330 (BASF)

( B ) Isocyanate-based thermosetting agent (B-1) A compound represented by Chemical Formula 7-1 (VESTANAT B-series, Degussa Corporation)

[Chemical Formula 7-1]

(B-1) a compound represented by Chemical Formula 8-1 (Degussa Corporation)

[Chemical Formula 8-1]

( C ) Binder Resin (C-1) Acrylic Binder Resin (CF-1106, and Photochemical Co., Ltd.) (C-2) Carbide Binder Resin (V259ME, Nippon Steel Chemical Co., Ltd. (NIPPON) STEEL CHEMICAL))

( D ) Photopolymerizable monomer (D-1) DPHA (Nippon KAYAKU) (D-2) Wesker 1000 (VISCOAT 1000) (Osaka Organic Chemical Industry Co., Ltd.)

( E ) Photopolymerization Initiator (E-1) SPI-03 (Samyang, Korea) (E-2) OXE01 (BASF)

( F ) Solvent Propylene glycol monomethyl ethyl acetate (PGMEA, Sigma-aldrich Copperation)

( G ) Other additives Fluoride-based surfactant (F-554, Dainippon Ink Chemical Industry Co., Ltd.)

[Table 2] (Unit: % by weight)

Evaluation

Manufacturing color filter samples

The photosensitive resin compositions according to Examples 1 to 5 and Comparative Examples 1 and 2 were respectively coated on a transparent square glass substrate (bare glass) to 3 μm by using a spin coater (K-Spin 8, KDNS). thick. The applied photosensitive resin composition was baked on a hot plate at 90 ° C for 120 seconds, exposed by an output (power) at 50 mJ using an exposer (I10C, Nikon Co.), and then The samples were post-baked in a forced convection oven at 230 ° C for 30 minutes.

Evaluation 1 : Evaluation of luminescence

The color characteristics of the color filter samples produced in Examples 1 to 5 and Comparative Examples 1 and 2 were additionally baked by a forced convection oven at 230 ° C for 30 minutes, and a spectrophotometer (Otsuka Electronics Co., Ltd.) was used. The company (Otsuka Electronics Co., Ltd.), MCPD3000) measured the color change before/after baking to measure, and the results are shown in Table 3.

Evaluation 2 : Evaluation of heat resistance

The heat resistance of the pattern of the color filter samples produced in Examples 1 to 5 and Comparative Examples 1 and 2 was measured by heat-treating them in an oven at 230 ° C for 30 minutes. The heat resistance was evaluated by the color change of the color filter pattern before and after the heat treatment, and the color change was measured using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD3000), and the results are shown in Table 3.

Evaluation 3 : Assess chemical resistance

The patterns of the color filter samples produced in Examples 1 to 5 and Comparative Examples 1 and 2 were immersed in an 80 ° C NMP solution for 5 minutes, and then the chemical resistance of the PI solution was evaluated. The chemical resistance was evaluated by the color change of the color filter pattern before and after immersion in the NMP solution and the peeling of the color filter pattern after being immersed in the release agent. The color change of the color filter pattern was measured using a spectrophotometer (Otsuka Electronics Co., Ltd., MCPD3000), and the peeling of the color filter pattern was evaluated by an optical microscope. The evaluation results are shown in Table 3.

[table 3]

As can be seen from Table 3, the dye polymers of Preparation Example 1 to Preparation Example 4 were included as compared with the photosensitive resin compositions having no dye polymer and isocyanate-based thermosetting agent according to Comparative Example 1 and Comparative Example 2, and according to Examples The photosensitive resin composition of the isocyanate-based thermosetting agent of 1 to 5 exhibited improved heat resistance and chemical resistance as well as color characteristics (for example, brightness).

Although the present invention has been described in connection with what is presently considered as a practical exemplary embodiment, it is understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover the spirit of the appended claims Various modifications and equivalent configurations within the scope. Therefore, the above embodiments are to be considered as illustrative and not restrictive.

no.

1 is a schematic view of a dye polymer having a core-shell structure in a photosensitive resin composition according to an embodiment.

Claims (16)

A photosensitive resin composition comprising: (A) a colorant comprising a dye polymer having a core-shell structure; (B) an isocyanate type heat hardener; (C) a binder resin; (D) a photopolymerizable single (E) a photopolymerization initiator; and (F) a solvent, wherein the dye polymer having the core-shell structure is a copolymer of a compound represented by Chemical Formula 1, a Rhodamine compound, and an acrylic compound: [Chemical Formula 1] Here, in Chemical Formula 1, R ⁰ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and n is an integer in the range of 3 to 30. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises: 5% by weight to 20% by weight, expressed by the chemical formula 1, based on the total amount of the copolymer a compound; 20% by weight to 60% by weight of the rhodamine-based compound; and 30% by weight to 70% by weight of the acrylic compound. The photosensitive resin composition according to claim 1, wherein the rhodamine-based compound contains a functional group represented by Chemical Formula 2 at the terminal: [Chemical Formula 2] Here, in Chemical Formula 2, R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group. The photosensitive resin composition according to claim 3, wherein the rhodamine compound is represented by Chemical Formula 3 or Chemical Formula 4: [Chemical Formula 3] [Chemical Formula 4] Wherein, in Chemical Formula 3 and Chemical Formula 4, R ² to R ^{6 are} independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or not a substituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, at least one of R ² to R ⁶ comprising a functional group represented by Chemical Formula 2, and X ⁻ from Chemical Formula A to Formula F A representation of: [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] PW ₁₂ O ₄₀ ^3- [Chemical Formula D] SiW ₁₂ O ₄₀ ^4- [Chemical Formula E] CF ₃ SO ₃ ^- [Chemical Formula F] ClO ₄ ^- . The photosensitive resin composition according to claim 1, wherein the acrylic compound is represented by Chemical Formula 5: [Chemical Formula 5] Wherein, in Chemical Formula 5, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and R ⁸ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, substituted or not Substituted C3 to C20 cycloalkyl or substituted or unsubstituted C6 to C20 aryl. The photosensitive resin composition according to claim 5, wherein the acrylic compound comprises a compound represented by Chemical Formula 5-1, a compound represented by Chemical Formula 5-2, and a compound represented by Chemical Formula 5-3. At least one compound selected: [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] Wherein, in Chemical Formula 5-1 to Chemical Formula 5-3, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and R ⁹ is a substituted or unsubstituted C3 to C20 cycloalkyl group, And R ¹⁰ is a substituted or unsubstituted C1 to C10 alkyl group. The photosensitive resin composition according to claim 1, wherein the dye polymer is a red dye polymer. The photosensitive resin composition according to claim 1, wherein the isocyanate-based thermosetting agent contains a blocked isocyanate group represented by Chemical Formula 6 at the terminal: [Chemical Formula 6] Wherein, in Chemical Formula 6, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group; An oxy group, a substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amine group. The photosensitive resin composition according to claim 8, wherein R ^{11 is} selected from the chemical formulas 6-1 to 6-8: [Chemical Formula 6-1] Wherein, in Chemical Formula 6-1, R ¹² is a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, [Chemical Formula 6-2] Wherein, in Chemical Formula 6-2, R ¹³ to R ^{15 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group, [Chemical Formula 6- 3] Wherein, in Chemical Formula 6-3, R ¹⁶ and R ^{17 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group, [Chemical Formula 6- 4] [Chemical Formula 6-5] Wherein, in Chemical Formula 6-5, R ¹⁸ to R ^{21 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group, [Chemical Formula 6- 6] Wherein, in Chemical Formula 6-6, R ²² and R ^{23 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group, [Chemical Formula 6- 7] Wherein, in Chemical Formula 6-7, R ²⁴ and R ^{25 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group, [Chemical Formula 6- 8] Wherein, in Chemical Formula 6-8, R ²⁶ and R ^{27 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C20 alkenyl group. The photosensitive resin composition according to claim 8, wherein the isocyanate-based thermosetting agent is represented by Chemical Formula 7 or Chemical Formula 8: [Chemical Formula 7] [Chemical Formula 8] Wherein, in Chemical Formula 7 and Chemical Formula 8, R ¹¹ is a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C6 To a C20 aryloxy group, a substituted or unsubstituted C2 to C20 heteroaryl group or a substituted or unsubstituted amine group, R ²⁸ to R ^{31 are} independently a substituted or unsubstituted C1 to C10 alkyl group. , L ¹ to L ^{12 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C3 to C20 cycloalkylene group, and m1 to m3 are independently 0 to An integer in the range of 4. The photosensitive resin composition according to claim 1, wherein the colorant further comprises a metal complex dye and a pigment. The photosensitive resin composition according to claim 11, wherein the amount of the dye polymer in the colorant is the total amount of the metal complex dye and the pigment in the colorant 0.1 to 5 times in the middle. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises: 10% by weight to 60% by weight of the coloring agent based on the total amount of the photosensitive resin composition (A); 0.1% by weight to 5% by weight of the isocyanate-based heat hardener (B); 1% by weight to 30% by weight of the binder resin (C); 1% by weight to 30% by weight of the light Polymerization monomer (D); 0.1% by weight to 8% by weight of the photopolymerization initiator (E); and the remaining amount of the solvent (F). The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition contains at least one additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, and a vinyl group. Or a coupling agent of a (meth) propylene oxirane, a leveling agent, a fluorine-based surfactant, and a radical polymerization initiator. A photosensitive resin layer is produced by using the photosensitive resin composition as described in any one of Claims 1 to 14. A color filter comprising the photosensitive resin layer according to item 15 of the patent application.