TWI641597B - Compound, photosensitive resin composition including the same and color filter - Google Patents

Abstract

The present invention discloses a compound represented by Chemical Formula 1, a photosensitive resin composition containing the compound, and a color filter produced using the photosensitive resin composition. [Chemical Formula 1] In Chemical Formula 1, each substituent is the same as defined in the detailed specification.

Description

Compound, photosensitive resin composition containing the same, and color filter

The present invention relates to a compound, a photosensitive resin composition comprising the compound, and a color filter.

Among many types of displays, liquid crystal display devices have the advantages of being light, thin, low in cost, low in operating power consumption, and high in adhesion to integrated circuits, and have been more widely used in laptops, monitors, and televisions. Screen. The liquid crystal display device includes a lower substrate and an upper substrate, and a black matrix, a color filter, and an indium tin oxide pixel electrode are formed on the lower substrate, and a liquid crystal layer, a thin film transistor, and a capacitor are formed on the upper substrate The active circuit portion of the layer and the indium tin oxide primitive electrode.

By sequentially stacking a plurality of color filters in a predetermined order (generally, formed by three primary colors (for example, red (R), green (G), and blue (B)) to form each primitive in the primitive area A color filter is formed in the medium, and a black matrix layer is disposed on the transparent substrate in a predetermined pattern to form a boundary between the respective primitives.

A pigment dispersion method as one of various methods of forming a color filter, which provides a colored film by repeating a series of processes: for example, coating a photopolymerizable composition containing a colorant on a transparent substrate including a black matrix Exposing the formed pattern; removing the unexposed portion with a solvent; and thermally curing it.

The colored photosensitive resin composition for producing a color filter according to the pigment dispersion method generally contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent, other additives, and the like, and further contains an epoxy resin or the like.

The pigment dispersion method is actively applied to the manufacture of liquid crystal displays such as mobile phones, laptops, monitors, and televisions. However, the photosensitive resin composition for a color filter using a pigment dispersion method having many advantages has some disadvantages in that it is difficult to finely pulverize the powder, and even if it is dispersed, various additives are required to stabilize the dispersion and it is required Complex processes and difficulty in further maintaining the optimum quality of the pigment dispersion under complex storage conditions and transport conditions.

Further, the color filter produced by using the pigment type photosensitive resin composition has limitations in brightness and contrast due to the fineness of the pigment. Therefore, there is a need to develop a dye having heat resistance and chemical resistance similar to those of a pigment.

Embodiments of the present invention provide a compound having improved solubility in an organic solvent and improved fluorescence quenching properties and spectroscopic coherence due to the form of a dimer having a functional linker. .

Another embodiment of the present invention provides a photosensitive resin composition comprising the compound.

According to still another embodiment of the present invention, a color filter manufactured using the photosensitive resin composition is provided.

An embodiment of the present invention provides a compound represented by Chemical Formula 1.

[Chemical Formula 1] In Chemical Formula 1, R ¹ to R ^{6 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and L ¹ is substituted or not. Substituted C1 to C20 alkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C6 to C20 arylene, *-OC(=O)NH-*, * -O(C=O)-*, *-NR ^X -* or a combination thereof, wherein R ^X is a substituted or unsubstituted C1 to C10 alkyl group, and X is represented by Chemical Formula X-1 or Chemical Formula X-2 .

L ¹ can be represented by Chemical Formula 2.

In Chemical Formula 2, L ² to L ^{6 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, *-OC (= O) NH-*, *-O(C=O)-* or *-NR ^X -*, wherein R ^X is a substituted or unsubstituted C1 to C10 alkyl group, the limitation of which is all L ² to L ^{6 is} not all single keys.

L ¹ may be a substituted or unsubstituted C1 to C20 alkylene group.

L ¹ can be represented by Chemical Formula 3.

[Chemical Formula 3] In Chemical Formula 3, L ⁷ to L ^{9 are} independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, or a combination thereof.

L ⁷ to L ⁹ may independently be a substituted or unsubstituted C1 to C10 alkylene group or represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

In Chemical Formula 3-1 and 3-2 in the formula, L ^a to L ^c are independently a substituted or unsubstituted C1 to C5 alkylene group.

L ¹ can be represented by Chemical Formula 4.

[Chemical Formula 4] In Chemical Formula 4, L ¹⁰ to L ^{12 are} independently a substituted or unsubstituted C1 to C10 alkylene group.

L ¹ can be represented by Chemical Formula 5.

[Chemical Formula 5] In Chemical Formula 5, L ¹³ and L ^{14 are} independently a substituted or unsubstituted C1 to C10 alkylene group, and R ^X is a substituted or unsubstituted C1 to C10 alkyl group.

At least one of R ¹ to R ⁴ may be represented by Chemical Formula 6-1 or Chemical Formula 6-2.

[Chemical Formula 6-1]

[Chemical Formula 6-2] In Chemical Formula 6-1 and Chemical Formula 6-2, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁵ and L ^{16 are} independently a substituted or unsubstituted C1 to C10 subunit. alkyl.

The compound represented by Chemical Formula 1 can be represented by one of Chemical Formula 7 to Chemical Formula 21.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 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 compound represented by Chemical Formula 1 has a maximum absorbance in a wavelength range of 500 nm to 600 nm.

Another embodiment of the present invention provides a photosensitive resin composition comprising the compound as a colorant.

The compound may be contained in an amount of from 5% by weight to 10% by weight based on the total amount of the photosensitive resin composition.

The compound can be a red dye or a blue dye.

The photosensitive resin composition may further contain a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The binder resin may include an acrylic binder resin, a card multi-adhesive resin, or a combination thereof.

The photosensitive resin composition may further contain a pigment as a colorant.

The photosensitive resin composition may include: 1% by weight to 10% by weight of the binder resin; and 5% by weight to 60% by weight of the coloring agent, based on the total amount of the photosensitive resin composition; 1% by weight to 10% by weight of the photopolymerizable compound; 0.01% by weight to 5% by weight of the photopolymerization initiator; and the balance of the solvent.

The photosensitive resin composition may further comprise malonic acid, 3-amino-1,2-propanediol, a decane-based coupling agent containing a vinyl group or a (meth)acryloxy group, a leveling agent, a surfactant, A radical polymerization initiator or a combination thereof.

Another embodiment of the present invention provides a color filter manufactured using the photosensitive resin composition.

Other embodiments of the invention are included in the detailed description which follows.

The solubility of the compound in an organic solvent according to the embodiment is improved and the fluorescence quenching property and the spectral coherence are improved, and thus a photosensitive resin composition containing a coloring agent (dye) containing the compound as a constituent element can be provided. A color filter with improved brightness, contrast, heat resistance and pattern characteristics.

Reference will now be made in detail to the exemplary embodiments embodiments Wherever possible, the same element symbols are used in the drawings and the description

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

As used herein, unless otherwise specified, "substituted" means that at least one hydrogen atom of a functional group of the invention is substituted with at least one substituent selected from the group consisting of: a halogen atom (F, Br, Cl 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 and independently are C1 to C10 alkyl), decyl, decyl, decyl, carboxy, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or not A substituted alicyclic organic group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group.

As used herein, unless otherwise specified, "alkyl" refers to C1 to C20 alkyl and especially to C1 to C15 alkyl, and "cycloalkyl" refers to C3 to C20 cycloalkyl and especially C3 to C18 naphthenic. The "alkoxy" means a C1 to C20 alkoxy group and especially a C1 to C18 alkoxy group, the "aryl group" means a C6 to C20 aryl group and especially a C6 to C18 aryl group, and the "alkenyl group" means a C2 group. To C20 alkenyl and especially C2 to C18 alkenyl, "alkylene" means C1 to C20 alkylene and especially C1 to C18 alkylene, and "arylene" means C6 to C20 arylene and especially C6 to C16 arylene.

As used herein, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "when" Methacrylic acid" both.

The term "combination" as used herein, when not otherwise defined, refers to mixing or copolymerization. Further, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymer.

As used herein, when no definition is provided, in the chemical formula, when a chemical bond is not drawn where it should be given, hydrogen bonding is at the position.

The cardoline resin as used herein refers to a resin comprising at least one functional group selected from the group consisting of Chemical Formula 17-1 to Chemical Formula 17-11 in its skeleton.

As used herein, "ethylene-unsaturated double bond" means "carbon-carbon double bond", and ethylenically unsaturated monomer means a monomer containing an ethylenically unsaturated double bond.

When a specific definition is not additionally provided, "*" as used herein means a point connecting the same or different atoms or chemical formulas.

An embodiment of the present invention provides a compound represented by Chemical Formula 1.

[Chemical Formula 1]

In Chemical Formula 1, R ¹ to R ^{6 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and L ¹ is substituted or not. Substituted C1 to C20 alkylene, substituted or unsubstituted C3 to C20 cycloalkylene, substituted or unsubstituted C6 to C20 arylene, *-OC(=O)NH-*, * -O(C=O)-*, *-NR ^X -* or a combination thereof, the R ^X is a substituted or unsubstituted C1 to C10 alkyl group, and X is from the chemical formula X-1 or the chemical formula X-2 Said.

[Chemical Formula X-1]

[Chemical Formula X-2]

As described above, the color filter produced using the pigment type photosensitive resin composition has limitations in brightness and contrast due to the fineness of the pigment. In addition, color image sensor devices for image sensors require smaller dispersed particle sizes to form fine patterns. In order to meet the above requirements, a color filter which is improved in brightness and contrast has been attempted by introducing a dye which does not form particles instead of a pigment to prepare a photosensitive resin composition suitable for a dye.

In general, a photosensitive resin composition containing a xanthene-based compound in which a charge is separated has a very low solubility to an organic solvent such as propylene glycol methyl ether acetate, and exhibits heat resistance and chemical resistance deterioration, and thus is colored. The use of the xanthene-based compound of the agent in the photosensitive resin composition is limited. However, the compound according to the embodiment (that is, the compound represented by Chemical Formula 1) can improve the solubility in an organic solvent, and additionally has a dimeric structure linked by a functional linking group and thus has excellent fluorescence quenching properties. And spectral coherence, and as a result, the photosensitive resin composition containing the compound can improve the brightness and contrast of the color filter.

For example, L ¹ can be represented by Chemical Formula 2.

In Chemical Formula 2, L ² to L ^{6 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, *-OC (= O) NH-*, *-O(C=O)-* or *-NR ^X -*, wherein R ^X is a substituted or unsubstituted C1 to C10 alkyl group, the limitation of which is all L ² to L ^{6 is} not all single button.

For example, L ¹ can be a substituted or unsubstituted C1 to C20 alkylene group.

For example, L ¹ can be represented by Chemical Formula 3.

[Chemical Formula 3]

In Chemical Formula 3, L ⁷ to L ^{9 are} independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, or a combination thereof.

For example, L ⁷ to L ⁹ may be independently a substituted or unsubstituted C1 to C10 alkylene group or represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[Chemical Formula 3-1]

[Chemical Formula 3-2]

In Chemical Formula 3-1 and 3-2 in the formula, L ^a to L ^c are independently a substituted or unsubstituted C1 to C5 alkylene group.

For example, L ¹ can be represented by Chemical Formula 4.

[Chemical Formula 4]

In Chemical Formula 4, L ¹⁰ to L ^{12 are} independently a substituted or unsubstituted C1 to C10 alkylene group.

For example, L ¹ can be represented by Chemical Formula 5.

[Chemical Formula 5]

In Chemical Formula 5, L ¹³ and L ^{14 are} independently a substituted or unsubstituted C1 to C10 alkylene group, and R ^X is a substituted or unsubstituted C1 to C10 alkyl group.

For example, at least one of R ¹ to R ⁴ may be represented by Chemical Formula 6-1 or Chemical Formula 6-2. For example, at least one of R ¹ to R ⁴ may be a substituted C1 to C10 alkyl group.

[Chemical Formula 6-1]

[Chemical Formula 6-2]

In Chemical Formula 6-1 and Chemical Formula 6-2, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁵ and L ^{16 are} independently substituted or unsubstituted C1 to C10. Alkylene.

For example, one of R ¹ to R ⁴ may be represented by Chemical Formula 6-1 or Chemical Formula 6-2.

For example, two of R ¹ to R ⁴ may be represented by Chemical Formula 6-1 or Chemical Formula 6-2.

For example, one of R ¹ and R ² and one of R ³ and R ⁴ may be represented by Chemical Formula 6-1 or Chemical Formula 6-2.

When at least one of R ¹ to R ⁴ is represented by Chemical Formula 6-1 or Chemical Formula 6-2, the solubility in an organic solvent can be further improved.

When at least one of R ¹ to R ⁴ is represented by Chemical Formula 6-1 or Chemical Formula 6-2, copolymerization may be carried out between the compound represented by Chemical Formula 1 and a monomer to form a polymer. For example, the monomer can be an ethylenically unsaturated monomer, and the polymer can be an acrylic polymer.

For example, the ethylenically unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated aminoalkyl carboxylate compound, a vinyl carboxylate compound, an unsaturated glycidyl carboxylate. A compound, a vinyl cyanide compound, an unsaturated guanamine compound, or a combination thereof.

For example, the ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylic acid ester compound, for example (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; aminoalkyl ester compound of unsaturated carboxylic acid, for example ( 2-aminoethyl methacrylate, 2-dimethylaminoethyl (meth) acrylate, etc.; carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl benzoate, etc.; unsaturated carboxylic acid glycidyl An ester compound such as glycidyl (meth)acrylate or the like; an acrylonitrile compound such as (meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth)acrylamide or the like or a combination thereof.

The acrylic polymer as a polymerization reaction product in which the compound represented by Chemical Formula 6-1 or Chemical Formula 6 represented by Chemical Formula 6-1 or the ethylenically unsaturated monomer is copolymerized with at least one of R ¹ to R ⁴ has an improved heat resistance And processability, and it can be used as a coloring agent (for example, a dye) in a photosensitive resin composition for a color filter.

The compound represented by Chemical Formula 1 may be represented by one of Chemical Formula 7 to Chemical Formula 21, but is not limited thereto.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical Formula 10]

[Chemical Formula 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 compound represented by Chemical Formula 1 has a maximum absorbance in a wavelength range of 500 nm to 600 nm.

Another embodiment provides a photosensitive resin composition containing the compound as a colorant.

The compound may be contained in an amount of 5 to 10% by weight (for example, 6 to 9 wt%, for example, 6 to 8 wt%) based on the total amount of the photosensitive resin composition, and thus Brightness, heat resistance and pattern characteristics can be further improved.

The compound can be a red dye or a blue dye.

The photosensitive resin composition may further contain a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Hereinafter, each component will be specifically described.

Colorant

The colorant may further contain an organic solvent-soluble dye in addition to the compound represented by Chemical Formula 1.

Examples of the organic solvent-soluble dye may be a triarylmethane-based compound, an anthraquinone-based compound, a benzylidene-based compound, a cyanine-based compound, a phthalocyanine-based compound, an azaporphyrin-based compound, and an indigo-based compound. Compounds, etc.

The colorant may further contain a pigment in addition to the compound represented by Chemical Formula 1.

The pigment may include a blue pigment, a violet pigment, a red pigment, a green pigment, a yellow pigment, and the like.

Examples of the blue pigment may be Pigment Index (CI) Blue Pigment 15:6, CI Blue Pigment 15, CI Blue Pigment 15:1, CI Blue Pigment 15:2, CI Blue Pigment 15:3 CI blue pigment 15:4, CI blue pigment 15:5, CI blue pigment 16, CI blue pigment 22, CI blue pigment 60, CI blue pigment 64, CI blue pigment 80 or a combination thereof.

Examples of the violet pigment may be CI violet pigment 1, CI violet pigment 19, CI violet pigment 23, CI violet pigment 27, CI violet pigment 28, CI violet pigment 29, CI violet pigment 30, CI violet pigment 32, CI violet Pigment 37, CI violet pigment 40, CI violet pigment 42, CI violet pigment 50, or a combination thereof.

Examples of the red pigment may be an anthraquinone pigment, an anthraquinone pigment, a diterpene pigment, an azo pigment, a diazo pigment, a quinacridone pigment, an anthraquinone pigment, or the like. Specific examples of the red pigment may be an anthraquinone pigment, a quinacridone pigment, a naphthol AS, a sicomin pigment, a samarium (sudan I, II, III, R), a diterpene ester. (dianthraquinonylate), bis azo, benzopyran, etc.

Examples of the green pigment may be a halogenated phthalocyanine-based pigment such as C.I. Pigment Green 58, C.I. Pigment Green 59 and the like.

Examples of the yellow pigment may include C.I. Pigment Yellow 139, C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, and the like, and may be used singly or in the form of a mixture of two or more.

The pigment may be contained in the photosensitive resin composition in the form of a pigment dispersion.

The pigment dispersion may contain a solid pigment, a solvent, and a dispersant that uniformly disperses the pigment in a solvent.

It may comprise from 1% by weight to 20% by weight, for example from 8% by weight to 20% by weight, for example from 8% by weight to 15% by weight, for example from 10% by weight to 20% by weight, for example 10, based on the total amount of the pigment dispersion The pigment in a solid content of from 5% by weight to 15% by weight.

The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant or the like. Specific examples of the dispersant may be polyalkylene glycol and esters thereof, polyoxyalkylenes, polyol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonate esters, sulfonates, carboxylates The acid ester, the carboxylate, the alkylguanamine alkylene oxide addition product, the alkylamine, and the like, and these dispersants may be used singly or in the form of a mixture of two or more.

Commercially available examples of the dispersant may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK made by BYK Co., Ltd. -161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; Evka Chemical Company ( EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, manufactured by EFKA Chemicals Co., and manufactured by Zeneka Co. Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or PB711 made by Ajinomoto Inc. PB821.

The dispersant may be included in an amount of from 1% by weight to 20% by weight based on the total weight of the pigment dispersion. When the dispersant in the above range is contained, the dispersion of the photosensitive resin composition is improved by an appropriate viscosity, and thus the optical quality, physical quality, and chemical quality can be maintained when the photosensitive resin composition is applied to a product. .

The solvent used to form the pigment dispersion may be ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether or the like.

The color former may be contained in an amount of from 5% by weight to 60% by weight (for example, from 6% by weight to 55% by weight) based on the total amount of the photosensitive resin composition. When the coloring agent within the range is included, color reproducibility is improved and the curability and close contact properties of the pattern are improved.

Adhesive resin

The binder resin may be an acrylic binder resin, a card multi-adhesive resin, or a combination thereof. For example, the binder resin may be an acrylic binder resin.

The acrylic adhesive resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group. 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 of from 5% by weight to 50% by weight (for example, from 10% by weight to 40% by weight) based on the total of the acrylic binder resin.

The second ethylenically unsaturated monomer may be 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.; unsaturated aminoalkyl carboxylate compound, such as 2-aminoethyl (meth)acrylate, 2-(meth)acrylate Dimethylaminoethyl ester or the like; a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; an unsaturated glycidyl carboxylate compound such as glycidyl (meth)acrylate; acrylonitrile; a compound such as (meth)acrylonitrile or the like; an unsaturated guanamine compound such as (meth) acrylamide or the like; and the like, and the second ethylenically unsaturated monomer may be used alone or in both or More is used in the form of a mixture.

Specific examples of the acrylic adhesive resin may be polybenzyl methacrylate copolymer, acrylic acid/methacrylic benzyl ester 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/methyl 2-hydroxyethyl acrylate copolymer, etc., but not limited thereto. These acrylic adhesive resins may be used singly or in the form of a mixture of two or more.

The acrylic binder resin may have a weight average molecular weight of from 3,000 g/mol to 150,000 g/mol (eg, from 5,000 g/mol to 50,000 g/mol, such as from 20,000 g/mol to 30,000 g/mol). When the weight average molecular weight of the acrylic adhesive resin is within the above range, the photosensitive resin composition has good physical properties and chemical properties, appropriate viscosity, and properties in close contact with the substrate during the manufacture of the color filter.

The acrylic binder resin may have an acid value of from 15 mgKOH/g to 60 mgKOH/g (for example, from 20 mgKOH/g to 50 mgKOH/g). When the acid value of the acrylic adhesive resin is within the above range, the primitive pattern can have excellent resolution.

The card multi-adhesive resin may contain a repeating unit represented by Chemical Formula 22.

[Chemical Formula 22]

In Chemical Formula 22, R ¹¹ and R ^{12 are} independently a hydrogen atom or a substituted or unsubstituted (meth) acryloxyalkyl group, and R ¹³ and R ^{14 are} independently a hydrogen atom, a halogen atom or a substituted Or unsubstituted C1 to C20 alkyl group, and Z ¹ is a single bond, O, CO, SO ₂ , CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ (wherein R ¹⁵ to R ^{18 are} independently a hydrogen atom or substituted Or an unsubstituted C1 to C20 alkyl group or one of the linking groups represented by Chemical Formula 22-1 to Chemical Formula 22-11.

[Chemical Formula 22-1]

[Chemical Formula 22-2]

[Chemical Formula 22-3]

[Chemical Formula 22-4]

[Chemical Formula 22-5]

Here, in Chemical Formula 22-5, 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 22-6]

[Chemical Formula 22-7]

[Chemical Formula 22-8]

[Chemical Formula 22-9]

[Chemical Formula 22-10]

[Chemical Formula 22-11]

Z ² is an acid dianhydride residue, and m1 and m2 are independently an integer ranging from 0 to 4.

The card multi-adhesive resin may contain a functional group represented by Chemical Formula 23 at at least one terminal.

[Chemical Formula 23]

In Chemical Formula 23, Z ³ can be represented by Chemical Formula 23-1 to Chemical Formula 23-7.

[Chemical Formula 23-1]

In Chemical Formula 23-1, R ^b and R ^{c are} independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group or an ether group.

[Chemical Formula 23-2]

[Chemical Formula 23-3]

[Chemical Formula 23-4]

[Chemical Formula 23-5]

In Chemical Formula 23-5, 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 alkenylamino group.

[Chemical Formula 23-6]

[Chemical Formula 23-7]

The cardo-based binder resin can be prepared, for example, by mixing at least two of the following compounds: a ruthenium-containing compound such as 9,9-bis(4-oxiranylmethoxyphenyl)anthracene (9,9-) Bis(4-oxiranylmethoxyphenyl)fluorene); anhydride compounds such as pyromellitic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutyl Alkanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride and tetrahydrophthalic anhydride; diol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; alcohol compounds such as methanol, ethanol, Propyl alcohol, n-butanol, cyclohexanol and benzyl alcohol; solvent-based compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as four Methyl ammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride.

When a cardo-based adhesive resin is used together with an acrylic-based adhesive resin, a photosensitive resin composition having excellent close contact force, high resolution, and high brightness characteristics can be obtained.

The card multi-adhesive resin may have a weight average molecular weight of from 500 g/mol to 50,000 g/mol (for example, from 3,000 g/mol to 30,000 g/mol). When the weight average molecular weight of the card multi-adhesive resin is within the range, a satisfactory pattern can be formed during the production of the color filter without residue, and the film thickness does not decrease during development.

The cardo binder resin may have an acid value of from 100 mgKOH/g to 140 mgKOH/g.

The binder resin may be contained in an amount of from 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the binder resin in the range is contained, excellent developability and sensitivity can be maintained and undercut can be prevented.

Photopolymerizable compound

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

The photopolymerizable compound may cause sufficient polymerization during exposure of the pattern forming process due to the ethylenic unsaturated double bond and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable compound may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(a) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A Di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, quaternary pentaerythritol hexa(meth)acrylate, dipentaerythritol Di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy (meth) acrylate , ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (methyl) propylene methoxyethyl phosphate, phenolic epoxy (meth) acrylate, etc. .

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

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

The photopolymerizable compound may be contained in an amount of from 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable compound in the range is contained, the photopolymerizable compound is sufficiently cured during exposure of the pattern forming process and has excellent reliability, and thus can be formed to have excellent heat resistance, light resistance, and chemical resistance. And excellent resolution and pattern of close contact properties.

Photopolymerization initiator

The photopolymerization initiator may be a photopolymerization initiator commonly used in the photosensitive resin composition, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an anthraquinone-based compound, or the like.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone (2- Hydroxy-2-methylpropiophenone), p-tert-butyltrichloroacetophenone, 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-? Polinylphenyl)-butan-1-one and the like.

Examples of the benzophenone compound may be benzophenone, benzhydryl benzoate, benzhydryl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic acid. Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylamino Benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthiophene Tons of ketone, 2-chlorothioxanthone, etc.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal, and the like.

Examples of the triazine-based 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 (three Chloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s- Triazine, 2-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol 1-yl)-4,6-double (trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperidinyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4 -Methoxystyryl)-s-triazine and the like.

An example of the lanthanoid compound may be an O-indenyl lanthanide compound, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione , 1-(O-ethylindolyl)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, O-ethoxy Carbonyl-α-oxoamino-1-phenylpropan-1-one and the like. A specific example of the O-mercapto lanthanide compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4 -yl-phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione 2-indole-O-benzoate, 1-(4- Phenylthiophenyl)-octane-1,2-dione 2-indole-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetic acid Ester, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and the like.

In addition to the above-mentioned compound, the photopolymerization initiator may further contain an oxazole compound, a diketone compound, a lanthanum borate compound, a diazo compound, an imidazole compound, a biimidazole compound, an anthraquinone compound, or the like. .

The photopolymerization initiator can be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and being excited and then transmitting its energy.

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

The photopolymerization initiator may be contained in an amount of from 0.01% 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, excellent reliability can be ensured due to sufficient curing during exposure of the pattern forming process, and the pattern can have excellent resolution and close contact properties as well as excellent heat resistance and light resistance. Sex and chemical resistance, and can prevent a decrease in transmittance due to a non-reactive initiator.

Solvent

The solvent is a material having compatibility with, but not reacting with, the compound according to the examples, the pigment, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.

Examples of the solvent may include an alcohol such as methanol, ethanol, etc.; an ether such as dichloroethyl ether, n-butyl ether, diisoamyl ether, anisole, tetrahydrofuran or the like; a glycol ether such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc.; cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; carbitol, such as methyl ethyl carbitol, two Ethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, etc.; propylene glycol alkyl ether acetate Esters 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-pentyl Ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate Ester, isobutyl acetate, etc.; lactate, such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetate, such as methyl oxyacetate, ethyl oxyacetate, Butyl oxyacetate or the like; alkyl alkoxyacetate such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Et.; alkyl 3-oxopropionate, such as methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.; alkyl 3-alkoxypropionate, such as 3-methoxypropane Methyl ester, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionate, such as 2-oxyl Methyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, 2-methoxy Ethyl propyl propionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionate, such as 2-oxy-2-methyl Methyl propionate, ethyl 2-oxy-2-methylpropionate, etc.; monoalkyl monocarboxylic acid alkyl ester of 2-alkoxy-2-methylpropionic acid alkyl ester, such as 2-A Methyl oxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Ester, ethyl hydroxyacetate, 2-hydroxy-3-methyl Methyl butyrate or the like; a keto ester such as ethyl pyruvate or the like. In addition, high boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di can also be used. Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, caproic acid, octanoic acid, 1-octanol, 1- Sterol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl acetate Fiber, etc.

In view of miscibility and reactivity, a ketone such as cyclohexanone or the like; a glycol ether such as ethylene glycol monoethyl ether or the like; a glycol alkyl ether acetate such as ethyl cellosolve acetate, etc. may be preferably used. An ester such as ethyl 2-hydroxypropionate or the like; a carbitol such as diethylene glycol monomethyl ether or the like; a propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate or propylene glycol propyl ether acetate; .

The solvent is used in the balance, and is, for example, 30% by weight to 70% by weight based on the total amount of the photosensitive resin composition. When the solvent in the range is contained, the coating property of the photosensitive resin composition is improved, and a film having improved flatness can be obtained.

Other additives

The photosensitive resin composition may further contain an additive such as malonic acid; 3-amino-1,2-propanediol; a decane-based coupling agent having reactivity such as a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group. Substituent; leveling agent; fluorine-based surfactant; radical polymerization initiator, etc., to prevent stains or spots during coating, to adjust leveling or to prevent pattern residue due to undeveloped.

Examples of the decane-based coupling agent may include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ - Isocyanatopropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These decane-based coupling agents may be used singly or in the form of a mixture of two or more.

The decane-based coupling agent may be contained in an amount of from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the decane-based coupling agent in the range is contained, the close contact property, the storage property, and the like can be improved.

The photosensitive resin composition may further contain an epoxy compound to improve properties in close contact with the substrate.

Examples of the epoxy compound may include a phenol novolac epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be contained in an amount of from 0.01 part by weight to 20 parts by weight (for example, from 0.1 part by weight to 10 parts by weight) per 100 parts by weight of the photosensitive resin composition. When the epoxy compound in the range is contained, the close contact property, the storage property, and the like can be improved.

Further, if necessary, the photosensitive resin composition may further contain a surfactant to improve coating properties and prevent defects.

The surfactant may be a fluorine-based surfactant, and an example of the fluorine-based surfactant may be F-482, F-484, F-478 of DIC Co., Ltd. F-554, etc., but not limited to this.

The surfactant may be used in an amount of from 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant in the range is contained, excellent wettability and coating uniformity on the glass substrate can be ensured, but no stain can be generated.

Further, the photosensitive resin composition may contain a predetermined amount of other additives such as an antioxidant, a stabilizer, or the like, unless other additives deteriorate the properties of the photosensitive resin composition.

According to another embodiment, a color filter manufactured using the photosensitive resin composition is provided.

The pattern forming process of the color filter is as follows.

The process includes: applying a positive photosensitive resin composition on a support substrate by spin coating, slit coating, inkjet printing, or the like; drying the applied positive photosensitive resin composition to form photosensitivity a resin composition film; exposing the positive photosensitive resin composition film; developing the exposed positive photosensitive resin composition film in an alkaline aqueous solution to obtain a photosensitive resin film; and heat-treating the photosensitive resin film. The conditions of the patterning process are well known in the relevant art and will not be described in detail in this specification.

The invention is described in more detail below with reference to examples, however, these examples should not be construed as limiting the scope of the invention in any way.

(synthesis of compounds)

Synthesis example 1 : by chemical formula 7 Synthesis of the indicated compound

Add 56 g of 2-propanol and 2.9 g of diethylamine to 8.1 g of 3',6'-dichlorospiro[3H-2,1-benzoxathiol-3,9'-[9H The mixture was stirred in the -1,1-dioxide and the mixture was stirred at room temperature for 3 hours. The precipitate was obtained with ether and dried to obtain Intermediate 1. 0.5 equivalent of N,N'-dimethyl-1,6-hexanediamine and water were added to the intermediate 1, and then reacted with the intermediate 1 at 80 ° C for one day to obtain a total yield of 47%. A compound represented by Chemical Formula 7.

[Chemical Formula 7] Matrix-assisted laser desorption ionization-Time of Flight (Maldi-tof) mass spectrometry (MS): 954 m/z

Synthesis example 2 : by chemical formula 8 Synthesis of the indicated compound

Except that N,N'-diethyl-1,6-hexanediamine was used instead of N,N'-dimethyl-1,6-hexanediamine in the reaction of Synthesis Example 1, according to Synthesis Example 1. The compound represented by Chemical Formula 8 was obtained by the same method.

[Chemical Formula 8] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 982 m/z

Synthesis example 3 : by chemical formula 9 Synthesis of the indicated compound

Intermediate 2 was obtained in the same manner as in Synthesis Example 1, except that 2-(ethylamino)ethanol was used instead of N,N'-dimethyl-1,6-hexanediamine of Synthesis Example 1. The compound represented by Chemical Formula 9 was obtained using a catalytic amount of dibutyltin dilaurate and 1,6-diisocyanatohexane with Intermediate 2.

[Chemical Formula 9] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1156 m/z

Synthesis example 4 : by chemical formula 10 Synthesis of the indicated compound

A compound represented by Chemical Formula 10 was obtained by the same method as in Synthesis Example 3, except that octanehydrin chloride was used instead of the 1,6-diisocyanatohexane of Synthesis Example 3.

[Chemical Formula 10] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1126 m/z

Synthesis example 5 : by chemical formula 11 Synthesis of the indicated compound

A chemical formula was obtained in the same manner as in Synthesis Example 3, except that 1,3-bis(isocyanatomethyl)-cyclohexane was used instead of the 1,6-diisocyanatohexane of Synthesis Example 3. Compound represented by 11.

[Chemical Formula 11] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1182 m/z

Synthesis example 6 : by chemical formula 12 Synthesis of the indicated compound

The compound represented by Chemical Formula 12 was obtained by adding an excess of thionyl chloride to the compound of Chemical Formula 7 in Synthesis Example 1 and refluxing the mixture to replace with sulfoyl chloride. An anionic portion of the sulfonic acid, and then the resulting product is reacted with 2 equivalents of trifluoromethanesulfonamide.

[Chemical Formula 12] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1216 m/z

Synthesis example 7 : by chemical formula 13 Synthesis of the indicated compound

The compound represented by Chemical Formula 13 was obtained in the following manner: a compound obtained according to the same method as in Synthesis Example 1 and an isocyanato group were used except that 2-(ethylamino)ethanol was used instead of diethylamine as a starting material. Ethyl methacrylate is reacted in a chloroform solvent.

[Chemical Formula 13] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1296 m/z

Synthesis example 8 : by chemical formula 14 Synthesis of the indicated compound

The compound represented by Chemical Formula 14 was obtained in the following manner: a compound obtained by the same reaction as in Synthesis Example 2 and an isocyanatoethylmethyl group were used except that 2-(ethylamino)ethanol was used instead of diethylamine. The acrylate is reacted under a chloroform solvent.

[Chemical Formula 14] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1325 m/z

Synthesis example 9 : by chemical formula 15 Synthesis of the indicated compound

The compound represented by Chemical Formula 15 was obtained in the same manner as in Synthesis Example 1, except that 1,4,7-trimethyldiethylenetriamine was used instead of N,N'-dimethyl-1,6-hexanediamine. Compound.

[Chemical Formula 15] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 907 m/z

Synthesis example 10 : by chemical formula 16 Synthesis of the indicated compound

A compound represented by Chemical Formula 16 was obtained in the same manner as in Synthesis Example 3 except that dicyclohexylmethane-4,4'-diisocyanate was used instead of 1,6-diisocyanatohexane.

[Chemical Formula 16] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1251 m/z

Synthesis example 11 : by chemical formula 17 Synthesis of the indicated compound

A compound represented by Chemical Formula 17 was obtained by the same method as in Synthesis Example 8 except that isopropyl chlorobenzene was used instead of the isocyanatoethyl methacrylate.

[Chemical Formula 17] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1122 m/z

Synthesis example 12 : by chemical formula 18 Synthesis of the indicated compound

The compound represented by Chemical Formula 18 was obtained in the same manner as in Synthesis Example 8 except that methacrylic acid chlorobenzene was used instead of the isocyanatoethyl methacrylate.

[Chemical Formula 18] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1151 m/z

Synthesis example 13 : by chemical formula 19 Synthesis of the indicated compound

Add 56 g of 2-propanol and 1.46 g of diethylamine to 8.1 g of 3',6'-dichlorospiro[3H-2,1-benzooxathiol-3,9'-[9H]xanthene In the -1,1-dioxide, and the mixture was stirred at room temperature for 3 hours. A precipitate was obtained with ether and then dried to obtain Intermediate 1.

Add 56 g of 2-propanol and 1.78 g of 2-(ethylamino)ethanol to 8.1 g of 3',6'-dichlorospiro[3H-2,1-benzooxathiol-3,9'- [9H]xanthene-1,1-dioxide, and the mixture was stirred at room temperature for 3 hours. A precipitate was obtained with ether and then dried to obtain Intermediate 2.

The intermediate 1 and the intermediate 2 were mixed in an amount of 1 equivalent, respectively, and the mixture was reacted with 1 equivalent of N,N'-diethyl-1,6-hexanediamine, and The compound thus obtained is reacted with acrylonitrile chloride to obtain a compound represented by Chemical Formula 19.

[Chemical Formula 19] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1053 m/z

Synthesis example 14 : by chemical formula 20 Synthesis of the indicated compound

A compound represented by Chemical Formula 20 was obtained by the same method as in Synthesis Example 13 except that methacrylic acid chlorobenzene was used instead of propylene chlorobenzene.

[Chemical Formula 20] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1067 m/z

Synthesis example 15 : by chemical formula twenty one Synthesis of the indicated compound

The compound represented by Chemical Formula 21 was obtained in the same manner as in Synthesis Example 13 except that the isocyanatoethyl methacrylate was used instead of the acrylonitrile.

[Chemical Formula 21] Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 1154 m/z

Comparative Synthesis Example 1 : Synthesis of a compound represented by Chemical Formula X

10 g of Compound A (CAS No. 77545-45-0) was placed in the reactor and dissolved in 100 g of 2-propanol. 7.2 g of diethylamine was added thereto, and the mixture was stirred at 80 ° C for 8 hours. The reactant was cooled, and 800 mL of water was added thereto to form a precipitate. The precipitate was subjected to inhale-filtering and additionally washed with water. The product filtered therefrom was dried to obtain 9.9 g of the compound represented by Chemical Formula X (yield: 84%). Matrix-assisted laser desorption ionization-time-of-flight mass spectrometry analysis: 478.2 m/z

Evaluation 1 : Solubility

0.5 g of each compound represented by Chemical Formula 7 to Chemical Formula 21 and Chemical Formula X was separately added to a dilution solvent (MeOH, CH ₂ Cl ₂ , cyclohexanone), and a rotary mixer (mixed rotor) at 25 ° C and 100 rpm (Mixrotar) VMR-5, Iuchi Seieido Co., Ltd.) Each solution was stirred for 1 hour, and then the dissolved state of each compound (the amount of compound dissolved in the solvent) The test was performed, and the results are shown in Table 1.

Solubility Evaluation Reference X: Solubility is less than 1% by weight ○: Solubility is greater than or equal to 1% by weight and less than 5% by weight ◎: Solubility is greater than or equal to 5% by weight

[Table 1]

(Synthesis of photosensitive resin composition)

Instance 1

The photosensitive resin compositions according to Examples 1 to 13, Comparative Examples 1 to 3, Reference Example 1, and Reference Example 2 were prepared by mixing the following components having the compositions shown in Tables 2 to 4.

Specifically, the photopolymerization initiator was dissolved in a solvent, and the solution was stirred at room temperature for 2 hours, to which a binder resin and a photopolymerizable compound were added, and the mixture was allowed to stand at room temperature. Stirred for 2 hours. Subsequently, a compound represented by Chemical Formula 5 and a pigment (pigment dispersion) were added as a coloring agent to the reactant, and the mixture was stirred at room temperature for one hour. Then, each product obtained therefrom was filtered 3 times to remove impurities to prepare a photosensitive resin composition.

[Table 2] (unit weight%)

[table 3] (unit weight%)

[Table 4] (unit weight%)

(A) Adhesive resin Acrylic adhesive resin (methacrylic acid / benzyl methacrylate = 15 / 85 (w / w), weight average molecular weight = 22,000 g / mol, acid value = 100 mgKOH / g, Samsung SDI Co., Ltd. (Samsung SDI Co., Ltd.)

(B) Colorant (B-1) Compound (B-2) of Synthesis Example 1 Compound (B-3) of Synthesis Example 2 Compound (B-4) of Synthesis Example 3 Compound (B-5) of Synthesis Example 4 Compound (B-6) of Synthesis Example 5 Synthesis of Compound of Example 6 (B-7) Synthesis of Compound of Example 7 (B-8) Synthesis of Compound of Example 8 (B-9) Compound of Synthesis Example 9 (B-10) Compound (B-11) xanthene compound dispersion of Synthesis Example 10, RCP-24 (Wako Ltd.) (B-12) Comparative Compound 1 (B-13) Pigment Red 254 dispersion of Synthesis Example 1 (Sanyo Co., Ltd.)

(C) Photopolymerizable compound Dipentaerythritol hexaacrylate (DPHA, Sartomer)

(D) Photopolymerization initiator OXE-01 (BASF)

(E) Solvent propylene glycol monomethylether acetate (PGMEA, Sigma-Aldrich)

(F) Additive F-554 (10% diluted solution) (Di Ai Sheng Co., Ltd.)

Instance 12

The photosensitive resin composition according to Example 12 was prepared according to the same method as Example 1 by mixing the following components having the composition shown in Table 5.

[table 5] (unit weight%)

Instance 13

A photosensitive resin composition was prepared in the same manner as in Example 12 except that the compound of Synthesis Example 8 (the compound represented by Chemical Formula 14) was used instead of the compound of Synthesis Example 7 (the compound represented by Chemical Formula 13).

Instance 14

A photosensitive resin composition was prepared in the same manner as in Example 12 except that the compound of Synthesis Example 11 (the compound represented by Chemical Formula 17) was used instead of the compound of Synthesis Example 7 (the compound represented by Chemical Formula 13).

Instance 15

A photosensitive resin composition was prepared in the same manner as in Example 12 except that the compound of Synthesis Example 12 (the compound represented by Chemical Formula 18) was used instead of the compound of Synthesis Example 7 (the compound represented by Chemical Formula 13).

Comparative example 3

A photosensitive resin composition was prepared in the same manner as in Example 12 except that a red pigment (SC-P541-4214, Toyo Corporation) was used instead of the compound of Synthesis Example 7 (the compound represented by Chemical Formula 13).

Evaluation 2-1 : Measurement of brightness

The photosensitive resin compositions according to Examples 1 to 11, Comparative Example 1, Comparative Example 2, Reference Example 1 and Reference Example 2 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, respectively, and The plate was dried on a hot plate at 90 ° C for 2 minutes to obtain a film. The entire surface of the film was exposed using a high pressure mercury lamp (50 mJ/cm ² ) having a dominant wavelength of 365 nm. Subsequently, the film was dried (post-baked, PSB) in a forced convection drying oven at 230 ° C for 30 minutes to obtain a sample. The color coordinates (Rx, Ry) and luminance (Y) of the primitive layer were measured using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 6. The reference color coordinate (Rx) is used to calculate the brightness (Y).

[Table 6]

Evaluation 2-2 : Measurement of brightness

The photosensitive resin compositions according to Example 12 to Example 15 and Comparative Example 3 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, and dried on a hot plate at 90 ° C for 2 minutes to obtain membrane. The film was exposed using a high pressure mercury lamp having a dominant wavelength of 365 nm. Subsequently, the film was dried in a forced convection drying oven at 200 ° C for 5 minutes to obtain a sample. The color coordinates and luminance (Y) of the primitive layer were measured using a spectrophotometer (MCPD3000, Otsuka Electronics Co., Ltd.), and the results are shown in Table 7. The reference color coordinate (Ry) is used to calculate the brightness (Y).

[Table 7]

Table 1 shows that the photosensitive resin composition of Examples 12 to 15 containing the compound (dye) according to the examples exhibited excellent brightness as compared with the photosensitive resin composition of Comparative Example 3.

Evaluation 3 : Measurement of heat resistance

The photosensitive resin compositions according to Examples 1 to 11, Comparative Example 1, Comparative Example 2, Reference Example 1 and Reference Example 2 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, respectively, and The plate was dried on a hot plate at 90 ° C for 2 minutes to obtain a film. The entire surface of the film was exposed using a high pressure mercury lamp (50 mJ/cm ² ) having a dominant wavelength of 365 nm. Subsequently, the film was dried (post-baked, PSB) in a forced convection drying oven at 230 ° C for 20 minutes to obtain a sample. The heat resistance was measured by calculating ▽(E*) based on the color change values before and after post-baking, and the results are shown in Table 8.

[Table 8]

Evaluation 4 : patterning ability ( Patternability )Measurement

The photosensitive resin compositions according to Examples 1 to 11, Comparative Example 1, Comparative Example 2, Reference Example 1 and Reference Example 2 were coated to a thickness of 1 μm to 3 μm on a 1 mm thick degreased glass substrate, respectively, and The plate was dried on a hot plate at 90 ° C for 2 minutes to obtain a film. Having a dominant wavelength of 365 nm using a high pressure mercury lamp (50 mJ / cm ²⁾ on the entire surface of the film was exposed and was developed to obtain a pattern. The developer was prepared by diluting a KOH solution manufactured by Hoimyung, and then the time (seconds) at which the pattern was displayed was monitored. (In this paper, BP should be measured as 25 seconds to 35 seconds, which makes it easy to apply to the actual process.) Drying the developed pattern substrate in a forced convection oven at 230 ° C (post-baking, PSB) 20 Minutes to complete the patterning. The pattern size (CD, based on 100 μm) of the patterned sample was measured by an optical microscope X500, and the results are shown in Table 9 and Figs. 1 and 2. (When the measured CD immediately after post-baking is 102 μm to 104 μm, it can be considered to have appropriate sensitivity.) The pattern tear is evaluated by an optical microscope as follows. ○: pattern circumference and close contact force are good △: pattern circumference is torn ×: pattern is layered

[Table 9]

The photosensitive resin composition according to the example exhibits excellent brightness, heat resistance, and patterning ability by including the compound represented by Chemical Formula 1 as a colorant (dye), as shown in Tables 6 to 9 and FIGS. 1 and 2 . . Specifically, when a compound represented by Chemical Formula 1 is used in an amount of less than 5% by weight based on the total amount of the photosensitive resin composition, even if the compound represented by Chemical Formula 1 is used as a colorant (dye), brightness is deteriorated. (The heat resistance is improved), and in addition, developability and patterning ability deteriorate as BP becomes longer. When the compound represented by Chemical Formula 1 is contained in an amount of more than 10% by weight based on the total amount of the photosensitive resin composition, the initial luminance is high but the heat resistance is poor, and thus the brightness after post-baking is drastically lowered and the patterning ability is further Deterioration. When the compound represented by Chemical Formula 1 is contained in an amount of less than 5% by weight or more than 10% by weight based on the total amount of the photosensitive resin composition, the sensitivity is remarkably deteriorated.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover the scope of the accompanying claims. Various modifications and equivalent configurations within the spirit and scope.

no

1 is a pattern photograph of a sample produced using the photosensitive resin composition according to Example 2. 2 is a pattern photograph of a sample produced using the photosensitive resin composition according to Comparative Example 2.

Claims (14)

A compound represented by Chemical Formula 1: Wherein, in Chemical Formula 1, R ¹ to R ^{6 are} independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group or a substituted or unsubstituted C6 to C20 aryl group, and L ¹ is substituted or Unsubstituted C6 to C20 alkylene group or represented by Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5, Wherein, in Chemical Formula 3, L ⁷ to L ^{9 are} independently a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C10 cycloalkylene group, or a combination thereof, [Chemical Formula 4] ] Wherein, in Chemical Formula 4, L ¹⁰ to L ^{12 are} independently a substituted or unsubstituted C1 to C10 alkylene group, Wherein, in Chemical Formula 5, L ¹³ and L ^{14 are} independently a substituted or unsubstituted C1 to C10 alkylene group, and R ^X is a substituted or unsubstituted C1 to C10 alkyl group, and X is a chemical formula X-1 or chemical formula X-2, The compound of claim 1, wherein L ⁷ to L ^{9 are} independently a substituted or unsubstituted C1 to C10 alkylene group or represented by Chemical Formula 3-1 or Chemical Formula 3-2: Wherein, in the chemical formulas 3-1 and 3-2 in the formula, L ^a to L ^c are independently a substituted or unsubstituted C1 to C5 alkylene group. The compound of claim 1, wherein at least one of R ¹ to R ⁴ is represented by Chemical Formula 6-1 or Chemical Formula 6-2: Wherein, in Chemical Formula 6-1 and Chemical Formula 6-2, R ⁷ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹⁵ and L ^{16 are} independently substituted or unsubstituted C1 To C10 alkylene. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by one of Chemical Formula 7 to Chemical Formula 21: [Chemical Formula 7] [Chemical Formula 15] [Chemical Formula 19] The compound according to claim 1, wherein the compound represented by Chemical Formula 1 has a maximum absorbance in a wavelength range of from 500 nm to 600 nm. A photosensitive resin composition comprising the compound according to item 1 of the patent application. The photosensitive resin composition according to claim 6, wherein the compound is contained in an amount of from 5% by weight to 10% by weight based on the total amount of the photosensitive resin composition. The photosensitive resin composition as described in claim 6, wherein the compound is a red dye or a blue dye. The photosensitive resin composition according to the sixth aspect of the invention, wherein the photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The photosensitive resin composition according to claim 9, wherein the binder resin comprises an acrylic binder resin, a cardo binder resin, or a combination thereof. The photosensitive resin composition as described in claim 9, wherein the photosensitive resin composition further contains a pigment as a coloring agent. The photosensitive resin composition according to claim 11, wherein the photosensitive resin composition contains: 1% by weight to 10% by weight of the adhesive, based on the total amount of the photosensitive resin composition a resin; 5% by weight to 60% by weight of the coloring agent; 1% by weight to 10% by weight of the photopolymerizable compound; 0.01% by weight to 5% by weight of the photopolymerization initiator; The solvent. The photosensitive resin composition according to claim 9, wherein the photosensitive resin composition further comprises malonic acid, 3-amino-1,2-propanediol, and contains vinyl or (meth) propylene hydride. An oxane-based coupling agent, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof. A color filter produced by using the photosensitive resin composition as described in claim 6 of the patent application.