TW201800839A - A blue photosensitive resin composition, blue color filter and display device comprising the same - Google Patents

Abstract

To provide a blue photosensitive resin composition, and a blue color filter and a display device comprising the same. This invention relates to a blue photosensitive resin composition with excellent adhesion, comprising a blue colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent; and a blue color filter and a display device comprising the same.

Description

Cyan photosensitive resin composition, cyan color filter including the same, and display device

Field of invention

The present invention relates to a cyan photosensitive resin composition, a cyan color filter and a display device including the same, and more particularly, to a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, A cyan photosensitive resin composition having excellent adhesion, a cyan color filter including the same, and a display device.

Background of the invention

As electronic display devices used in office automation equipment, portable small TVs, camera viewfinders, etc., there are a liquid crystal display (LCD), a plasma display panel (PDP), and an organic light emitting diode. Organic light emitting diodes (OLEDs), etc., are actively conducting technical research related to these.

The above-mentioned liquid crystal display device has weight reduction, thinness, low price, low power consumption driving, and excellent bonding with integrated circuits, etc. The advantage is that the range of use is increasing in notebook personal computers, monitors, and television graphics. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit portion including a liquid crystal layer, a thin film transistor, and a storage capacitor layer, and an upper substrate on which the ITO pixel electrode is formed. Make up.

The color filter is manufactured by applying a fine region colored with three or more colors on a solid-state imaging element or a transparent substrate. Such a colored film is generally formed by a dyeing method, an electrodeposition method, a pigment dispersion method, and the like, but recently a pigment dispersion method having excellent heat resistance and durability has been used.

The pigment dispersion method is a method of forming a colored film by applying a series of processes of coating a photopolymerizable composition containing a colorant on a transparent substrate provided with a light-shielding layer (black matrix), exposure, development, and thermal curing. The pigment dispersion method has the advantages that heat resistance and durability, which are the most important properties of a color filter, can be improved, and the thickness of the film can be uniformly maintained.

The coloring photosensitive resin composition used in the manufacture of a color filter using the pigment dispersion method is generally composed of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives.

In recent years, high color reproduction of a color filter is required, and thus the content of the coloring agent of the coloring photosensitive resin composition used in the production of the color filter is continuously increasing. In addition, in order to produce high-quality color filters with excellent visibility, improvement of contrast is continuously required.

However, in the conventional pigment dispersion system, the content of the pigment in the colored photosensitive resin composition has reached its limit, and the improvement in contrast due to the micronization of the pigment has also reached the limit. From this, today, researched A method of using both a pigment and a dye as a colorant. However, if a color filter is produced using a colored photosensitive resin composition containing a dye, the sensitivity is insufficient, and a problem arises in that the pattern formed during the development process using an alkali developer is peeled off. In addition, when a color filter is manufactured using a coloring photosensitive resin composition containing a dye, problems such as insufficient compatibility of the dye in the hard baking process, precipitation of the dye on the surface, and reduction in contrast arise.

Summary of invention

An object of the present invention is to provide a cyan photosensitive resin composition that does not suffer from a decrease in sensitivity due to a dye and is excellent in adhesion even though the dye is used in a minimum amount.

Another object of the present invention is to provide a cyan photosensitive resin composition capable of displaying high transmission and high contrast.

Furthermore, an object of the present invention is to provide a cyan color filter and a display device manufactured using the cyan photosensitive resin composition.

To achieve the above object, the present invention provides a cyan photosensitive resin composition, which is a cyan photosensitive resin composition including a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and is characterized in that The cyan colorant includes a dye of the following chemical formula 1, and the photopolymerization initiator includes a compound of the following chemical formula 2.

[Chemical Formula 1]

The R ₁ to R ₆ are the same or different, and are hydrogen, an aryl group having 6 to 12 carbon atoms with or without a substituent, or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is Oxygen may be contained between the methylene groups, and the hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted by a halogen atom or an amine group. The above R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively The groups R ₇ to R ₁₄ are the same or different, and are each a hydrogen, a halogen atom, a nitro group, a sulfofluorenyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the alkyl group having 1 to 8 carbon atoms. The group may include oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms with or without a substituent, and the X is oxygen, sulfur, Or an amine group, the Y is a counter anion, and the m is an oxidation number of Y.

[Chemical Formula 2]

The a and b are 0 or 1, when the a is 1, the b is 1, and when the a is 0, the b is 0 or 1. (1) When the a = 0 and b = 0, the R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group substituted or unsubstituted with a halogen atom, a phenylsulfonyloxy group with or without a substituent, a halogen group Atomic substituted or unsubstituted sulfofluorenyl group having 1 to 8 carbon atoms, heterocyclic sulfofluorenyl group having 7 to 20 carbon atoms with or without substituents, or carbon number with or without substituents 7 to 20 fused cyclic sulfonyl groups, (2) in the case of a = 0 and b = 1, the above R ₁₆ is a phenyl group with or without a substituent, and a carbon number with or without a substituent A heterocyclic group of 7 to 20 or a fused ring group of 7 to 20 carbon atoms with or without substituents. (3) In the case of a = 1 and b = 1, R ₁₆ is a halogen atom. The substituted or unsubstituted sulfonyloxy group having 1 to 8 carbon atoms, or a phenylsulfonyloxy group containing or not having a substituent, the above-mentioned R ₁₇ and R ₁₈ are each the same or different and are hydrogen or carbon. 1 to 22 alkyl groups, 1 to 10 carbon alkyl groups containing a halogen atom, and the terminal is Carbon atoms, a thioether group or alkyl group having 1 to 15, with or without a substituted phenyl group, or a phenyl group having 7 to C 11, said R ₁₇ and R ₁₈ may form a ring, R ₁₉ above Is the following Chemical Formula 3 or Chemical Formula 4,

Each of the above R ₂₀ and R _{22 is the} same or different, and is an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an alkyl group having 2 to 7 carbon atoms at the end of which is an ether group or a thioether group. Group, phenyl group with or without substituents, phenylalkyl group with 7 to 11 carbon atoms with or without substituents, phenoxyalkyl group with 7 to 10 carbon atoms with or without substituents, containing Or a heterocyclic group having 7 to 20 carbons without a substituent or a fused ring group having 7 to 20 carbons with or without a substituent, wherein R ₂₁ is an alkyl group with 1 to 17 carbons, and contains halogen 1 to 7 carbon atoms of the atom, 2 to 7 carbon atoms of the ether or thioether group at the terminal, 2 to 4 carbon atoms of the amino group containing or not having a substituent, or not Substituted phenyl, 7 to 11 carbon phenyl alkyl group with or without substituents, 7 to 10 carbon phenyl alkyl group with or without ether at the end Group, a fused ring group having 7 to 20 carbon atoms with or without a substituent, or a heterocyclic group having 7 to 20 carbon atoms with or without a substituent, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbon atoms 1 to 6 carbons containing a halogen atom, with or without substituents Group, phenylalkyl group with 7 to 10 carbon atoms with or without substituents, phenylalkyl group with 7 to 9 carbon atoms with or without substituents at the end, with or without Condensed ring group having 7 to 20 carbon atoms with a substituent, or heterocyclic group having 7 to 20 carbon atoms with or without a substituent.

The present invention also provides a cyan color filter manufactured using the cyan photosensitive resin composition.

The present invention further provides a display device including the cyan color filter.

The cyan photosensitive resin composition of the present invention has an effect of being excellent in adhesion to a substrate, and does not cause a problem of peeling a pattern in a developing step.

In addition, the cyan photosensitive resin composition of the present invention can exhibit characteristics of high transmission and high contrast even though a dye is used in a minimum amount.

Furthermore, a color filter and a display device manufactured using the cyan photosensitive resin composition of the present invention have an effect of excellent color reproduction.

detailed description

The present invention is explained in more detail below.

The present invention relates to a cyan photosensitive resin composition, which is a cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the cyan colorant contains The dye of the following chemical formula 1, and the photoinitiator includes a compound of the following chemical formula 2.

The R ₁ to R ₆ are the same or different, and are hydrogen, an aryl group having 6 to 12 carbon atoms with or without a substituent, or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is Oxygen may be contained between the methylene groups, and the hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted by a halogen atom or an amine group. The above R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively The groups R ₇ to R ₁₄ are the same or different, and are each a hydrogen, a halogen atom, a nitro group, a sulfofluorenyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the alkyl group having 1 to 8 carbon atoms. The group may include oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms with or without a substituent, and the X is oxygen, sulfur, Or an amine group, the Y is a counter anion, and the m is an oxidation number of Y.

The a and b are 0 or 1, when the a is 1, the b is 1, and when the a is 0, the b is 0 or 1. (1) When the a = 0 and b = 0, the R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group which may be substituted or unsubstituted by a halogen atom, a phenylsulfonyloxy group with or without a substituent, Sulfonyl groups of 1 to 8 carbon atoms substituted or unsubstituted by halogen atoms, heterocyclic sulfonyl groups of 7 to 20 carbon atoms containing or not substituted, or carbons with or without substituents 7 to 20 fused cyclic sulfonyl groups, (2) in the case of a = 0 and b = 1, the above R ₁₆ is a phenyl group with or without a substituent, and a carbon with or without a substituent A heterocyclic group of 7 to 20 or a fused ring group of 7 to 20 carbon atoms with or without substituents. (3) In the case of a = 1 and b = 1, the above R ₁₆ is a halogen-containing group. The atomic substituted or unsubstituted sulfonyloxy group having 1 to 8 carbon atoms, or a phenylsulfonyloxy group containing or not having a substituent, the above-mentioned R ₁₇ and R ₁₈ are each the same or different and are hydrogen or carbon. 1 to 22 alkyl groups, 1 to 10 carbon alkyl groups containing a halogen atom, and the terminal is The alkyl group having 1 to 15 carbon atoms of the ether group or thioether group, a phenyl group containing or not having a substituent, or a phenyl alkyl group having 7 to 11 carbon atoms, the above R ₁₇ and R ₁₈ may form a ring, and the above R ₁₉ is the following Chemical Formula 3 or Chemical Formula 4,

Each of the above R ₂₀ and R _{22 is the} same or different, and is an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an alkyl group having 2 to 7 carbon atoms at the end of which is an ether group or a thioether group. Group, phenyl group with or without substituents, phenylalkyl group with 7 to 11 carbon atoms with or without substituents, phenoxyalkyl group with 7 to 10 carbon atoms with or without substituents, containing Or a heterocyclic group having 7 to 20 carbons without a substituent or a fused ring group having 7 to 20 carbons with or without a substituent, wherein R ₂₁ is an alkyl group with 1 to 17 carbons, and contains halogen 1 to 7 carbon atoms of the atom, 2 to 7 carbon atoms of the ether or thioether group at the terminal, 2 to 4 carbon atoms of the amino group containing or not having a substituent, or not Substituted phenyl, 7 to 11 carbon phenyl alkyl group with or without substituents, 7 to 10 carbon phenyl alkyl group with or without ether at the end Group, a fused ring group having 7 to 20 carbon atoms with or without a substituent, or a heterocyclic group having 7 to 20 carbon atoms with or without a substituent, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbon atoms 1 to 6 carbons containing a halogen atom, with or without substituents Group, phenylalkyl group with 7 to 10 carbon atoms with or without substituents, phenylalkyl group with 7 to 9 carbon atoms with or without substituents at the end, with or without Condensed ring group having 7 to 20 carbon atoms with a substituent, or heterocyclic group having 7 to 20 carbon atoms with or without a substituent.

In the present invention, a cyan photosensitive resin composition having excellent adhesion to a substrate and excellent developability is provided by including the dye of the above Chemical Formula 1 as a colorant and the compound of the Chemical Formula 2 as a photopolymerization initiator.

The following describes the properties of the cyan photosensitive resin composition of the present invention. Each component is explained in detail.

(A) Cyan colorant

The cyan colorant, which is one component of the cyan photosensitive resin composition of the present invention, contains a dye of the following Chemical Formula 1, and can further include a cyan pigment.

(a1) Cyan dye

The cyan colorant contains a cyan dye of the following Chemical Formula 1.

The R ₁ to R ₆ are the same or different, and are hydrogen, an aryl group having 6 to 12 carbon atoms with or without a substituent, or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is Oxygen may be contained between the methylene groups, and the hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted by a halogen atom or an amine group. The R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be each R ₇ to R ₁₄ are bonded to each other to form a ring. Each of the R ₇ to R _{14 is the} same or different, and is a hydrogen, a halogen atom, a nitro group, a sulfofluorenyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. The group may include oxygen between the methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms with or without a substituent, and the X is oxygen, sulfur, Or an amine group, the Y is a counter anion, and the m is an oxidation number of Y.

The Y is preferably one or more anions selected from the group consisting of boron, aluminum, sulfur, fluorine, tungsten, molybdenum, silicon, and phosphorus, and these anions can additionally include oxygen.

[Y] ^{m- of the} above Chemical Formula 1 may preferably be selected from the group consisting of anion of heteropolyacid containing tungsten, anion of isopolyacid containing tungsten, anion of phosphotungstic acid, anion of silicotungstic acid, and the same One of the anions of tungstic acid.

(kegging)型鎢磷酸離子，可列舉出α-[PW₁₂O₄₀]^3-，作為

(Dawson)型鎢磷酸離子，可列舉出α-[P₂W₁₈O₆₂]^6-和β-[P₂W₁₈O₆₂]^6-，作為

型鎢矽酸離子，可列舉出α-[SiW₁₂O₄₀]^4-、β-[SiW₁₂O₄₀]^4-、γ-[SiW₁₂O₄₀]^4-等，此外，可列舉出[P₂W₁₇O₆₁]^10-、[P₂W₁₅O₅₆]^12-、[H₂P₂W₁₂O₄₈]^12-、[NaP₅W₃₀O₁₁₀]^14-、α-[SiW₉O₃₄]^10-、γ-[SiW₁₀O₃₆]^8-、α-[SiW₁₁O₃₉]^8-、β-[SiW₁₁O₃₉]^8-、[W₆O₁₉]^2-、[W₁₀O₃₂]^4-、和WO₄ ^2-等。 [Y] ^{m- of the} above Chemical Formula 1, more specifically, for example, as

(kegging) -type tungsten phosphate ion, α- [PW ₁₂ O ₄₀ ] ^{3- can} be cited as

Examples of (Dawson) -type tungsten phosphate ions include α- [P ₂ W ₁₈ O ₆₂ ] ^6- and β- [P ₂ W ₁₈ O ₆₂ ] ^6- .

Examples of type tungsten silicic acid ions include α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4-, and the like, and [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- and WO ₄ ^2- and the like.

Furthermore, it is preferable that said m is a natural number of 1-15.

In addition, the cyan colorant can additionally use an acid dye selected from the group consisting of an acid dye having an acid group such as a sulfonic acid and a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of the acid dye, and the like, and derivatives thereof. In addition to the compounds, azo-based, xanthene-based, and phthalocyanine-based acid dyes and their derivatives may be selected. Among them, azo-based acid dyes and their derivatives are preferably used. In addition, it is preferable that the cyan dye includes a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a well-known dye described in a dyeing note (Seishinsha).

The above-mentioned dyes that can be used additionally, for example, as the CI solvent dye, CI solvent blue 5, 35, 36, 37, 44, 45, 59, 67, and 70; and CI solvent violet 8, 9 , 13, 14, 36, 37, 47, and 49.

Among these, one or more selected from C.I. Solvent Blue 35, 36, 44, 45, and 70; and C.I. Solvent Violet 13 are preferably contained.

Examples of the CI acid dye include CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, and 86. , 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285 , 290, 296, 315, 324: 1, 335, and 340; and CI Acid Violet 6B, 7, 9, 17, 19, and 66, etc.

Among them, it is preferably selected from the group consisting of C.I. Acid Blue 80 and 90; And one or more of C.I. Acid Violet 66.

Furthermore, examples of CI direct dyes include CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101 , 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170 , 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242 , 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, and 293; and CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, and 104.

Examples of CI mordant dyes include CI mordant blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31 , 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30 , 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, and 58.

These cyan dyes can be used individually or in combination of 2 or more types.

The cyan dye is contained in an amount of 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the total weight of the cyan colorant. Regarding the content of the cyan dye in the cyan colorant, In other words, if the content is 0.5 to 80% by weight, after the pattern is formed, the problem of reducing the reliability of the elution of the dye due to the organic solvent can be prevented, and the sensitivity can be improved.

(a2) Cyan pigment

The cyan pigment can be an organic pigment or an inorganic pigment generally used in this field. In addition, the cyan pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment of a pigment surface using a polymer compound, and the like, if necessary, using sulfuric acid. A micronization process such as a micronization method, a cleaning process using an organic solvent, water, or the like for removing impurities, or a ionic impurity removal process using an ion exchange method, or the like.

As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used. Specific examples include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinones. Pigments, Isoindoline Pigments, Perylene Pigments, Fluorenone Pigments, Dioxazine Pigments, Anthraquinone Pigments, Bisanthrenequinone Pigments, Anthrapyrimidine Pigments, Anthrone Pigments, Indanthrone Pigments, Xanthones Pigments, Dermatanthracenes Ketone pigments, diketopyrrolopyrrole pigments, and the like.

In addition, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, Metal oxides such as organic black pigments, titanium black, and pigments that mix red, green, and cyan to black, or mixed metal oxides.

In particular, as the above-mentioned organic pigments and inorganic pigments, Specifically, compounds classified as pigments in the Outstanding Index (published by The Society of Dyers and Colourists) can be listed, and more specifically, pigments having the following color index (C.I.) numbers can be listed, but are not necessarily limited to these.

Cyan pigments include, for example, CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, and 38; and CI Pigment Blue 15: 3, 15: 4, 15: 6, 21, 28, 60, 64, and 76.

Among these, one or more selected from C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, and Pigment Blue 15: 6 are preferably contained.

When the pigment is used in addition to the dye of Chemical Formula 1, the pigment is contained in an amount of 20 to 90% by weight, and preferably 30 to 70% by weight based on the total weight of the cyan colorant. When the pigment is contained in an amount of 20 to 90% by weight, the viscosity is low, the storage stability is excellent, the dispersion efficiency is improved, and the contrast can be increased.

As the pigment, a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed is preferably used. As an example of a method for uniformly dispersing the particle diameter of a pigment, a method of dispersing treatment containing a pigment dispersant (a3) may be mentioned. According to the above method, a state in which the pigment is uniformly dispersed in a solution can be obtained. Pigment dispersion.

(a3) Pigment dispersant

The pigment dispersant is added in order to maintain the deagglomeration and stability of the pigment. Specific examples of the pigment dispersant include positive ionization. Surfactants such as sub-systems, anionic systems, non-ionic systems, amphoteric systems, polyester systems, polyamine systems, and the like can be used individually or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, and alkyl sulfates such as sodium dodecyl sulfate and ammonium dodecyl sulfate. Salts, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and ethylene oxide / Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and poly Oxyethylene alkylamine and the like.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine modifications are exemplified. Polyurethanes and polyethyleneimines.

The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Department of dispersant). Examples of commercially available products of the acrylic dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. The acrylic dispersants can be used alone or in combination. More than one species is used.

The pigment dispersant may be other resin-based pigment dispersants in addition to the acrylate-based dispersant. Examples of the other resin-based pigment dispersants include known resin-based pigment dispersants, and in particular, polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamines, and polycarboxylic acids. Acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acids Esters and their modified products, or oily dispersants such as amidines or their salts formed by the reaction of a polyester having a free carboxyl group with poly (lower alkyleneimine); ( (Meth) acrylic-styrene copolymer, (meth) acrylic- (meth) acrylate copolymer, styrene-maleic acid copolymer, water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone or water-soluble Polymer compounds; polyesters; modified polyacrylates; ethylene oxide / propylene oxide addition products; and phosphate esters.

)化學公司的商品名：DISPER BYK-160、DISPER BYK-161、DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、DISPER BYK-182、DISPER BYK-184；BASF 公司的商品名：EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、EFKA-4400、EFKA-4406、EFKA-4510、EFKA-4800；Lubirzol公司的商品名：SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；川研精細化學株式會社的商品名：

(HINOACT)T-6000、

T-7000、

T-8000；味之素株式會社的商品名：

(AJISPUR)PB-821、

PB-822、

PB-823；共榮社化學株式會社的商品名：

(FLORENE)DOPA-17HF、

DOPA-15BHF、

DOPA-33、

DOPA-44等。 As a commercially available product of the other resin-based pigment dispersants, examples of the cationic resin dispersant include BYK (

) Trade names of chemical companies: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK- 184; Trade names of BASF companies: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Products of Kawaken Fine Chemicals name:

(HINOACT) T-6000,

T-7000,

T-8000; Trade name of Ajinomoto Co., Ltd .:

(AJISPUR) PB-821,

PB-822,

PB-823; Trade name of Kyoeisha Chemical Co., Ltd .:

(FLORENE) DOPA-17HF,

DOPA-15BHF,

DOPA-33,

DOPA-44 and so on.

In addition to the above-mentioned acrylate-based dispersant, other resin-based pigment dispersants can be used individually or in combination of two or more kinds, and can be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of 5 to 60 parts by weight, and preferably 15 to 50 parts by weight based on 100 parts by weight of the solid content in the pigment. When the content of the pigment dispersant exceeds 60 parts by weight, the viscosity will increase. If the content is less than 5 parts by weight, the micronization of the pigment may be difficult, and problems such as gelation after dispersion may occur.

In addition, the cyan colorant is contained in an amount of 5 to 60% by weight, and preferably 10 to 45% by weight, based on the total weight of the solid content in the cyan photosensitive resin composition. Contains 5 to 60% by weight of the above cyan In the case of a toner, when a thin film is formed, the color density of a pixel is sufficient, and the drop-off property of a non-pixel portion is not reduced during development, and residue is hardly generated.

In the present invention, the weight of the solid component in the cyan photosensitive resin composition means the total weight of the cyan photosensitive resin composition without the remaining components.

(B) Alkali soluble resin

The alkali-soluble resin as a component of the cyan photosensitive resin composition of the present invention is produced by copolymerizing an ethylenically unsaturated monomer (b1) containing a carboxyl group as an essential component.

Examples of the carboxyl group-containing ethylenically unsaturated monomer (b1) include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; Monocarboxylic acid anhydrides such as dicarboxylic acids; mono (meth) acrylates such as ω-carboxy polycaprolactone mono (meth) acrylate, and polymers containing a carboxyl group and a hydroxyl group at both ends; acrylic acid and methacrylic acid are preferred.

In order to ensure additional developability, a hydroxyl group can be added to the alkali-soluble resin.

Examples of the method for imparting the above-mentioned hydroxyl group include (1) a method of producing a copolymer of an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, and (2) a method of producing a glycidyl group A method for producing a compound by reacting a compound with a carboxyl group-containing ethylenically unsaturated monomer, and (3) adding a compound having a glycidyl group to an ethylenically unsaturated monomer having a carboxyl group and an olefin containing a hydroxyl group A method for producing a copolymer of an unsaturated monomer by reaction.

Specific examples of the hydroxyl-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( Among them, 2-hydroxy-3-phenoxypropyl methacrylate and N-hydroxyethylpropenamide are preferred. Among them, 2-hydroxyethyl (meth) acrylate is preferred, and the above-mentioned ethylenically unsaturated monomer containing a hydroxyl group is preferred. It can be used in combination of two or more kinds.

Specific examples of the glycidyl group-containing compound include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, Glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, 4-tert-butylbenzoic acid glycidyl ester, hard Glycidyl fatty acid, aryl glycidyl ether, and glycidyl methacrylate, etc., preferably, butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate, The glycidyl group-containing compound can be used in combination of two or more kinds.

In the production of the alkali-soluble resin, the unsaturated monomer that can be copolymerized with the carboxyl group-containing ethylenically unsaturated monomer includes aromatic vinyl compounds, N-substituted maleimide-based compounds, and alicyclics. Group (meth) acrylates, hydroxyethyl (meth) acrylates, aryl (meth) acrylates, unsaturated oxetane compounds, and the like are not limited to these.

Specific examples of the aromatic vinyl compound include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, and the like. O-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl Methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

Specific examples of the N-substituted maleimide-based compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N -O-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide Amine, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methyl Oxyphenylmaleimide, N-p-methoxyphenylmaleimide, and the like.

Specific examples of the alicyclic (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and iso (meth) acrylate. (Meth) acrylic acid alkyl esters such as propyl ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate; ( Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [meth) acrylate [5.2.1.02.6] decane-8-yl Esters, 2-dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

Specific examples of the hydroxyethyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , (Meth) acrylic 2-hydroxy-3-phenoxypropyl enoate, and N-hydroxyethylpropenamide and the like.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

Specific examples of the unsaturated oxetane compound include 3- (methacryloxymethyl) oxetane and 3- (methacryloxymethyl) -3- Ethyloxetane, 3- (methacryloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloxymethyl) -2-phenyl Oxetane, 2- (methacryloxymethyl) oxetane, and 2- (methacryloxymethyl) -4-trifluoromethyloxetane, etc. .

These unsaturated monomers can be used individually or in mixture of 2 or more types.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH / g in order to ensure compatibility with the dye and storage stability of the cyan photosensitive resin composition.

When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the cyan photosensitive resin composition is slow, and when it exceeds 150 mgKOH / g, the adhesion to the substrate is reduced, and short circuit of the pattern is likely to occur. There is a problem in compatibility with the dye, and the dye in the cyan photosensitive resin composition may be precipitated, the storage stability may be lowered, and the viscosity may be increased.

The alkali-soluble resin is contained in an amount of 10 to 80% by weight, and preferably 10 to 70% by weight, based on the total weight of the cyan photosensitive resin composition.

When the content of the alkali-soluble resin is 10 to 80% by weight, the solubility in the developing solution is sufficient, and the formation of a pattern is easy. During development, the film of the pixel portion of the exposed portion is prevented from being reduced, and the non-pixel portion has a good peeling property. .

(C) Photopolymerizable compound

The photopolymerizable compound as a component of the cyan photosensitive resin composition of the present invention must be a polymerizable compound under the action of a photopolymerization initiator (D) described later.

As a photopolymerizable compound, a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used, and a bifunctional monomer is preferably used, but it is not limited to this.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl acrylate Esters, or N-vinylpyrrolidone, but are not limited to these.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and Glycol di (meth) acrylate, bis (propylene ethoxyethyl) ether of bisphenol A, or 3-methylpentanediol di (meth) acrylate, and the like are not limited to these.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) Acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, or dipentaerythritol hexa (meth) acrylic acid Esters and the like are not limited to these.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, and preferably 7 to 50% by weight based on the total weight of the cyan photosensitive resin composition of the present invention. When the photopolymerizable compound is in the range of 5 to 50% by weight, the strength and reliability of the pixel portion can be made good.

(D) Photopolymerization initiator

The photopolymerization initiator as a component of the cyan photosensitive resin composition of the present invention includes a compound of the following Chemical Formula 2.

The a and b are 0 or 1, when the a is 1, the b is 1, and when the a is 0, the b is 0 or 1. (1) When the a = 0 and b = 0, the R ₁₆ is hydrogen, a halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group substituted or unsubstituted with a halogen atom, a phenylsulfonyloxy group with or without a substituent, a halogenated group Atomic substituted or unsubstituted sulfofluorenyl group having 1 to 8 carbon atoms, heterocyclic sulfofluorenyl group having 7 to 20 carbon atoms with or without substituents, or 7 carbon atoms with or without substituents ~ 20 fused ring sulfofluorenyl group, (2) in the case of a = 0, b = 1, the above R ₁₆ is a phenyl group with or without a substituent, and a carbon number of 7 with or without a substituent A heterocyclic group of ~ 20, or a fused ring group of 7 to 20 carbon atoms with or without a substituent, (3) In the case of a = 1 and b = 1, the above-mentioned R ₁₆ is substituted by a halogen atom. Or an unsubstituted sulfonyloxy group of an alkyl group having 1 to 8 carbon atoms, or a phenylsulfonyloxy group containing or not having a substituent, the above-mentioned R ₁₇ and R ₁₈ are each the same or different and are hydrogen and a carbon number of 1 Alkyl group ~ 22, alkyl group containing 1 to 10 carbon atoms including halogen atom, and ether group at the end Alkyl thioether group having a carbon number of 1 to 15, with or without a substituted phenyl group, or a phenyl group having 7 to C 11, said R ₁₇ and R ₁₈ may form a ring, R ₁₉ is the above-described Said Chemical Formula 3 or Chemical Formula 4,

[Chemical Formula 4]

Each of the above R ₂₀ and R _{22 is the} same or different, and is an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an alkyl group having 2 to 7 carbon atoms at the end of which is an ether group or a thioether group. Group, phenyl group with or without substituents, phenylalkyl group with 7 to 11 carbon atoms with or without substituents, phenoxyalkyl group with 7 to 10 carbon atoms with or without substituents, containing Or a heterocyclic group having 7 to 20 carbons without a substituent or a fused ring group having 7 to 20 carbons with or without a substituent, wherein R ₂₁ is an alkyl group with 1 to 17 carbons, and contains halogen 1 to 7 carbon atoms of the atom, 2 to 7 carbon atoms of the ether or thioether group at the terminal, 2 to 4 carbon atoms of the amino group containing or not having a substituent, or not Substituted phenyl, 7 to 11 carbon phenyl alkyl group with or without substituents, 7 to 10 carbon phenyl alkyl group with or without ether at the end Group, a fused ring group having 7 to 20 carbon atoms with or without a substituent, or a heterocyclic group having 7 to 20 carbon atoms with or without a substituent, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbon atoms 1 to 6 carbons containing a halogen atom, with or without substituents Group, phenylalkyl group with 7 to 10 carbon atoms with or without substituents, phenylalkyl group with 7 to 9 carbon atoms with or without substituents at the end, with or without Condensed ring group having 7 to 20 carbon atoms with a substituent, or heterocyclic group having 7 to 20 carbon atoms with or without a substituent.

The aforementioned R ₂₀ and R _{22 are} preferably methyl.

The compound of the above Chemical Formula 2 prevents a decrease in sensitivity and transmittance of a dye, and enables the cyan photosensitive resin composition of the present invention containing a dye as a colorant to effectively exhibit photopolymerization characteristics.

Examples of the compound of the above Chemical Formula 2 include commercially available UPI-03, UPI-22, and the like.

The compound containing the above Chemical Formula 2 contains 10 to 100% by weight, and preferably contains 20 to 100% by weight based on the total weight of the photopolymerization initiator.

If the compound of the above Chemical Formula 2 is contained in an amount of less than 10% by weight, a decrease in sensitivity due to a dye cannot be overcome, and a short circuit of a pattern is liable to occur in the developing step.

In addition, the photopolymerization initiator is preferably selected from the group consisting of acetophenone-based compounds and benzophenone in addition to the compound of Chemical Formula 2 from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. Compounds, triazine compounds, biimidazole compounds, and thioxanthone compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, and the like. 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- (Methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, and 2- (4-methylbenzyl) -2- (dimethylamino ) -1- (4-morpholinophenyl) butane-1-one and the like.

Specific examples of the benzophenone-based compound include benzophenone, 0-benzylmethylbenzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'- Methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, and 2,4- Bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3, 5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- 2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) Vinyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3, 5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2 , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2,2- Bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 4,4', 5,5 'phenyl are alkoxylated Carbonyl-substituted imidazole compounds and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) are preferably used. ) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1, 2'-biimidazole.

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4. -Propoxythioxanthone and the like.

The photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, and preferably 1 to 30% by weight, based on the total weight of the solid content in the cyan photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, the sensitivity of the cyan photosensitive resin composition is increased, the exposure time is shortened, productivity is improved, and high resolution can be maintained. In addition, the strength of the pixel portion and the smoothness of the surface of the pixel portion are improved.

The photopolymerization initiator may further include a photopolymerization initiation aid (d1) in order to increase the sensitivity of the cyan photosensitive resin composition of the present invention. By containing the photopolymerization initiation aid (d1) in the cyan photosensitive resin composition according to the present invention, the sensitivity is further improved, and productivity can be improved.

As the photopolymerization initiation aid, for example, one or more compounds selected from an amine compound and a carboxylic acid compound can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate; 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylamino group Ethyl ester, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as melidone) and 4,4'-bis (diethylamine) Di) benzyl Ketones, etc.

The carboxylic acid compound is preferably an aromatic heteroacetic acid. Specific examples include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthio. Acetic acid, dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, dimethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid and naphthyloxyacetic acid.

The photopolymerization initiation aid is contained in an amount of 0.1 to 40% by weight, and preferably 1 to 30% by weight based on the total weight of the solid content in the cyan photosensitive resin composition.

When the photopolymerization initiation aid is contained in an amount of 0.1 to 40% by weight, the sensitivity of the cyan photosensitive resin composition is improved, and the productivity of the color filter can be improved.

(E) Solvent

As long as the solvent is effective in dissolving other components contained in the cyan photosensitive resin composition, the solvent used in a general cyan photosensitive resin composition can be used without particular limitation, and ethers, acetates, and aromatics are particularly preferred. Groups of hydrocarbons, ketones, alcohols, esters, or amidines.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. ; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether such as diethylene glycol dialkyl Ethers, etc.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethyl Glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether ethyl Acid esters, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methylpentyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

Examples of the amidamines include dimethylformamidine Amine (DMF) and N-methyl-2-pyrrolidone (NMP).

These solvents can be used individually or in mixture of 2 or more types.

In terms of coating properties and drying properties, the solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C. Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, Ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The solvent is contained in an amount of 60 to 90% by weight, and preferably 70 to 85% by weight, based on the total weight of the cyan photosensitive resin composition. If the above-mentioned solvent is contained in the range of 60 to 90% by weight, a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and inkjet are used. When the coating device is applied, the coatability becomes good.

(F) Additives

The additive can be optionally added as needed, and can include, for example, one or more selected from the group consisting of antioxidants, other polymer compounds, curing agents, surfactants, adhesion promoters, ultraviolet absorbers, and anticoagulants.

The antioxidant may include one or more selected from a phenol-based antioxidant and a phosphorus-based antioxidant. In the case of a phenol-based antioxidant, it does not deteriorate in an oven at 150 ° C. for 200 hours or more.

The phenol-based antioxidant is preferably a hindered phenol-based antioxidant. Specific examples include 3- (3,5-di-tert-butyl-4-hydroxybenzene). Octadecyl propionate (Octadecyl3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (264 hours), 1,3,5-trimethyl-2,4,6- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (1,3,5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) benzene) (240 hours), and pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (Pentaerythritol tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) (960 hours) and so on.

Specific examples of the phosphorus-based antioxidant include triphenyl phosphate, isodecyl diphenyl phosphate, and tris (2,4-di-tert-butylphenyl) phosphate. ) Ester (Tris (2,4-di-tert-butylphenyl) phosphate), 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphospha Spiro [5.5] undecane (3,9-Bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane), and 2,2'-methylenebis (4 2,6-di-tert-butyl-phenyl) -2-ethylhexyl phosphate and the like.

The antioxidant is contained in an amount of 1 to 100 parts by weight, and preferably 2 to 50 parts by weight based on 100 parts by weight of the photopolymerization initiator. When the antioxidant is contained in an amount of 1 to 100 parts by weight, there is no reduction in sensitivity of the cyan photosensitive resin composition, and an improvement in transmittance can be expected. If the antioxidant is contained in an amount of less than 1 part by weight, it is difficult to expect an improvement in transmittance. If it exceeds 100 parts by weight, the sensitivity of the dye cannot be overcome. It is lowered, and sensitivity cannot be increased, and a short circuit of a pattern easily occurs in the development process.

Specific examples of the other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , Polyester, polyurethane and other thermoplastic resins.

The curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, Novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of epoxy resins, epoxy resins, and Aliphatic, alicyclic or aromatic epoxy compounds other than its brominated derivatives, butadiene (co) polymer epoxide, isoprene (co) polymer epoxide, (meth) acrylic acid Glycidyl ester (co) polymer, and triglycidyl isocyanurate.

Among the above curing agents, specific examples of the oxetane compound include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and p-benzene Diformate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

The said hardening | curing agent can be used together with a hardening | curing agent and the curing auxiliary compound which can ring-open and polymerize the epoxy group of an epoxy compound and the oxetane skeleton of an oxetane compound.

EH-700(

工業(株)製造)、

HH(新日本理化(株)製造)和MH-700(新日本理化(株)製造)等。上述例示的固化剂可以單独使用或者将2种以上混合使用。 Examples of the curing auxiliary compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. As the polybasic carboxylic acid anhydride, a product commercially available as an epoxy resin curing agent can be used. Examples of the above-mentioned commercial products include

EH-700 (

Industry Co., Ltd.),

HH (manufactured by Shin Nihon Chem. Co., Ltd.) and MH-700 (manufactured by Shin Nihon Chem. Co., Ltd.). The curing agent exemplified above may be used alone or as a mixture of two or more kinds.

In order to further improve the film formation of the cyan photosensitive resin composition, the above-mentioned surfactant can be used, and a silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, amphoteric surfactant, or the like is preferably used.

The above-mentioned silicone-based surfactants are, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF- 4445, TSF-4446, TSF-4460 and TSF-4452.

F-470、F-471、F-475、F-482和F-489等。 The fluorine-based surfactant is, for example, a commercially available product from Dainippon Ink Chemical Industry Co., Ltd.

F-470, F-471, F-475, F-482 and F-489.

(POLYFLOW)(共榮社化學(株))、

(EFTOP)(

社)、

(MEGAFAC)(大日本油墨化學工業(株))、

(Flourad)(住 友3M(株))、

(Asahi guard)、

(Surflon)(以上為旭硝子(株))、

(SOLSPERSE)(Lubrisol)、EFKA(EFKA化學公司)、PB 821(味之素(株))、Disperbyk系列(BYK-chemi)等。 In addition, as other commercially available products, KP (Shin-Etsu Chemical Industry Co., Ltd.),

(POLYFLOW) (Kyoeisha Chemical Co., Ltd.),

(EFTOP) (

Company),

(MEGAFAC) (Dai Nihon Ink Chemical Industry Co., Ltd.),

(Flourad) (Sumitomo 3M Co., Ltd.),

(Asahi guard),

(Surflon) (above are Asahi Glass Co., Ltd.),

(SOLSPERSE) (Lubrisol), EFKA (EFKA Chemical Company), PB 821 (Ajinomoto Co., Ltd.), Disperbyk series (BYK-chemi), and the like.

The surfactants exemplified above can be used individually or in combination of two or more kinds.

The type of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri (2-methyl) (Oxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

The adhesion promoters exemplified above can be used individually or in combination of two or more kinds. The adhesion promoter is usually contained in an amount of 0.01 to 10% by weight, and preferably 0.05 to 2% by weight based on the total weight of the solid content in the cyan photosensitive resin composition.

The type of the ultraviolet absorber is not particularly limited, and specific examples that can be used include 2- (3-tert-butyl-2-hydroxy Methyl-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

There is no particular limitation on the type of the above-mentioned anticoagulant, and specific examples of usable examples include sodium polyacrylate and the like.

The manufacturing method of the cyan photosensitive resin composition of this invention is as follows.

A cyan dye (a1), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) containing the above-mentioned Chemical Formula 1 are added, and an additive (F) is further added as necessary so that With a predetermined concentration, the cyan photosensitive resin composition according to the present invention can be produced.

When a pigment is contained as the cyan colorant, the cyan pigment (a2) and the solvent (E) are mixed and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, if necessary, a part or all of the pigment dispersant (a3) and the alkali-soluble resin (B) can be mixed with the solvent (E) to be dissolved or dispersed.

The remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D), and the additives (F) and solvents (E) used as necessary are further added to the above-mentioned mixed color. With a predetermined concentration, the cyan photosensitive resin composition according to the present invention can be produced.

The present invention also provides a cyan color filter made of a cyan photosensitive resin composition and a display device having the same.

First, a cyan photosensitive resin composition is applied to The substrate (usually glass) or the solid component of the cyan photosensitive resin composition formed previously is then dried by heating and removing volatile components such as solvents to obtain a smooth coating film.

As a coating method, for example, a spin coating, a cast coating method, a roll coating method, a slit, a spin coating, or a slit coating method can be used. After coating, it may be dried by heating (pre-baking), or dried under reduced pressure and then heated to volatilize volatile components such as solvents. Among them, the heating temperature is usually 70 to 200 ° C, and preferably 80 to 130 ° C. The thickness of the coating film after heating and drying is usually about 1 to 8 μm. The coating film thus obtained was irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, the entire exposure portion is uniformly irradiated with parallel light rays, and in order to accurately align the mask and the substrate, it is preferable to use a device such as a mask aligner and a stepper. When ultraviolet rays are irradiated, curing of the portions irradiated with ultraviolet rays is performed.

As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), and the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as required, and is not particularly limited in the present invention. The cured coating film is brought into contact with a developing solution, the non-exposed portion is dissolved, and development is performed to obtain a spacer having a desired pattern shape.

The development method is not particularly limited to a liquid addition method, a dipping method, a spray method, and the like. In addition, the substrate can be tilted at an arbitrary angle during development. The developing solution is usually an aqueous solution containing a basic compound and a surfactant.

The above-mentioned basic compound is not particularly limited to inorganic or organic Organic basic compounds. Examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, and silicic acid. Potassium, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic basic compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and the like. Triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine.

The above-mentioned inorganic or organic basic compounds can be used individually or in combination of two or more kinds. The concentration of the basic compound in the developing solution is 0.01 to 10% by weight, and preferably 0.03 to 5% by weight relative to the total weight of the developing solution.

As the surfactant in the developing solution, one or more selected from the above-mentioned nonionic surfactants, anionic surfactants, and cationic surfactants can be used. The concentration of the surfactant in the developing solution is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight with respect to the total weight of the developing solution. After development, it is washed with water, and if necessary, post-baking can be performed at 150 to 230 ° C for 10 to 60 minutes.

Using the cyan photosensitive resin composition of the present invention, a specific pattern can be formed on a substrate through each of the steps described above.

Hereinafter, in order to specifically describe the present invention, examples will be described in detail. However, the embodiments according to the present invention may be modified into various In various forms, the scope of the invention should not be construed as being limited to the examples detailed below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Synthesis example 1. Synthesis of alkali-soluble resin

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the nitrogen atmosphere was substituted. 100 parts by weight of propylene glycol monomethyl ether acetate was charged, and heated to 85 ° C. while stirring. .

Next, in the above flask, 19 parts by weight of methacrylic acid and 3,4-epoxytricyclo [5.2.1.02.6] decane-8- Mixture of 3,4-epoxytricyclo [5.2.1.02.6] decane-9-yl acrylate (Molar ratio of 50:50) (trade name "E-DCPA", Daicel Corporation (Production) 171 parts by weight of a solution dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate.

Using another dripping pump, about 5 hours, 26 parts by weight of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether ethyl. A solution of 120 parts by weight of an acid ester. After the dripping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then it was cooled to room temperature to obtain a 43.5% alkali-soluble resin solution containing a solid content of the monomers of the following Chemical Formulas 5, 6, and 7.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin are measured under the following conditions using a GPC measurement method.

Moreover, the ratio (Mw / Mn) of polystyrene conversion weight average molecular weight and number average molecular weight was made into a molecular weight distribution.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL / min

Solid content concentration of test liquid: 0.001 ~ 0.01% by weight

Injection volume: 50 μL

Detector: RI

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The weight-average molecular weight of the obtained alkali-soluble resin was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mgKOH / g.

<Synthesis of Cyan Dyes>

Synthesis Example 2.

2-1.

This reaction is carried out under a nitrogen atmosphere.

After putting 36.3 parts by weight of potassium thiocyanate and 160 parts by weight of acetone into a flask having a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts by weight of benzamidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes.

After the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction mixture was ice-cooled, and then 45.7 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was stirred at normal temperature for 30 minutes.

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at normal temperature for 30 minutes. Then, 35.3 parts by weight of chloroacetic acid was added dropwise at room temperature. After the dropwise addition was completed, the mixture was stirred under reflux for 7 hours.

Next, after the reaction mixture was allowed to cool to normal temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution, and the mixture was stirred. 30 minutes. Then, it was left to stand for 30 minutes, and the reaction mixture was separated into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was evaporated and removed with an evaporator, and a pale yellow liquid was obtained. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 52 parts by weight of a compound of the following Chemical Formula 8 (yield: 50%).

2-2.

This reaction is carried out under a nitrogen atmosphere.

9.3 parts by weight of the compound of Chemical Formula 8 produced in the above Synthesis Example 2-1 and 4,4'-bis (diethylamino) benzophenone (Tokyo Chemical Industry Co., Ltd.) were put into a flask having a cooling tube and a stirring device. (Production) 10 parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C for 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then diluted with 170 parts by weight of isopropyl alcohol. Then, 300 parts by weight of saturated saline was poured into the diluted reaction solution, and then 100 parts by weight of toluene was added, followed by stirring for 30 minutes. The stirring was stopped, and the mixture was left for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

The obtained organic layer was evaporated and removed with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts by weight of a compound of the following Chemical Formula 9 Rate 100%).

Mass analysis of compound of chemical formula 9

Ionization mode: ESI ⁺ : m / z = 601.3 [M-Cl] ⁺

Accurate mass: 636.3

2-3.

This reaction is carried out under a nitrogen atmosphere.

Into a flask having a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 9 produced in the above Synthesis Example 2-2, and 4.5 parts by weight of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged. And 100 parts by weight of N, N-dimethylformamide, and then stirred at 50 to 60 ° C for 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then dropped into 2000 parts by weight of tap water while stirring for 1 hour to obtain a dark cyan suspension. The suspension obtained above was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60 ° C to obtain 11.3 parts by weight of a compound of the following Chemical Formula 10 (yield: 82%).

The compound of the above formula is dissolved in chloroform 0.35g 10, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with ion-exchanged water, so that the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz Cell and optical path length; 1 cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 10 showed an absorbance of 2.9 at λmax = 628 nm.

Synthesis Example 3.

3-1.

2 parts by weight of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 50 parts by weight of methanol. Then, 15.41 parts by weight of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts by weight of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at 65 ° C. for 8.5 hours.

The mixture was cooled to normal temperature, and then a precipitate was obtained by suction filtration and washed with 237 parts by weight of ion-exchanged water to obtain 10.9 parts by weight of a compound of the following Chemical Formula 11.

3-2.

This reaction is carried out under a nitrogen atmosphere.

10 parts by weight of the compound of Chemical Formula 9 synthesized in the above Synthesis Example 2-2, 5.3 parts by weight of the compound of Chemical Formula 11 synthesized in the above Synthesis Example 3-1, and N, N- After 100 parts by weight of dimethylformamide, the mixture was stirred at 50 to 60 ° C for 3 hours.

Next, after cooling the reaction mixture to room temperature, stir While stirring for 1 hour, 2,000 parts by weight of tap water was added dropwise to obtain a dark cyan suspension. The suspension was filtered to obtain a cyan-green solid, and the cyan-green solid was dried under reduced pressure at 60 ° C to obtain 12 parts by weight of a compound of the following Chemical Formula 12 (yield: 83%).

The compound of the above formula is dissolved in chloroform 0.35g 12, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with ion-exchanged water, so that the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz Cell and optical path length; 1 cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 12 showed an absorbance of 2.6 at λmax = 628 nm.

Synthesis Example 4.

This reaction is carried out under a nitrogen atmosphere.

A flask having a cooling tube and a stirring device was charged with 10 parts by weight of the compound of Chemical Formula 9 synthesized in the above Synthesis Example 2-2, 14.1 parts by weight of tungsten silicic acid hydrate (manufactured by SIGMA-ALDRICH), and N, N- After 100 parts by weight of dimethylformamide, the mixture was stirred at 50 to 60 ° C for 3 hours.

Next, after cooling the reaction mixture to room temperature, stir While stirring for 1 hour, 2,000 parts by weight of tap water was added dropwise to obtain a dark cyan suspension. The suspension was filtered to obtain a cyan-green solid, and the cyan-green solid was dried under reduced pressure at 60 ° C to obtain 17.3 parts by weight of a compound of the following Chemical Formula 13 (yield: 83%).

The compound of the above formula is dissolved in chloroform 0.35g 13, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with ion-exchanged water, so that the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz Cell and optical path length; 1 cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 13 showed an absorbance of 1.5 at λmax = 628 nm.

Synthesis Example 5.

5-1.

This reaction is carried out under a nitrogen atmosphere.

After putting 32.2 parts by weight of potassium thiocyanate and 160 parts by weight of acetone into a flask having a cooling tube and a stirring device, the mixture was stirred at room temperature. 30 minutes. Then, 50 parts by weight of 2-fluorobenzidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped for 10 minutes.

After the dropwise addition, the mixture was stirred at normal temperature for 2 hours, and the reaction mixture was ice-cooled, and then 40.5 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was stirred at normal temperature for 30 minutes.

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at normal temperature for 30 minutes. Then, 31.3 parts by weight of chloroacetic acid was added dropwise at normal temperature. After the dropwise addition was completed, the mixture was stirred under reflux for 7 hours.

Next, after cooling the reaction mixture to normal temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution, and the mixture was stirred for 30 minutes. Then, it was left to stand for 30 minutes, and the reaction mixture was separated into an organic layer and an aqueous layer.

After the water layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was removed by evaporating the solvent using an evaporator, and a pale yellow liquid was obtained. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 49.9 parts by weight (yield 51%) of the compound of the following Chemical Formula 14.

[Chemical Formula 14]

5-2.

This reaction is carried out under a nitrogen atmosphere.

9.9 parts by weight of the compound of the chemical formula 14 produced in the above Synthesis Example 5-1 and 4,4'-bis (diethylamino) benzophenone (Tokyo Kasei Co., Ltd.) were put into a flask having a cooling pipe and a stirring device. (Made by the company) 10 parts by weight and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C for 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then diluted with 170 parts by weight of isopropyl alcohol. Then, 300 parts by weight of saturated saline was poured into the diluted reaction solution, and then 100 parts by weight of toluene was added, followed by stirring for 30 minutes. The stirring was stopped, and the mixture was left for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

The obtained organic layer was evaporated and removed with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts by weight of a compound of the following Chemical Formula 15 (received). Rate 85%).

Mass Analysis of Compound of Chemical Formula 15

Ionization mode: ESI ⁺ : m / z = 619.3 [M-Cl] ⁺

Accurate mass: 654.3

5-3.

This reaction is carried out under a nitrogen atmosphere.

Into a flask having a cooling tube and a stirring device, 10 parts by weight of the compound of Chemical Formula 15 produced in the above Synthesis Example 5-2, and 5.7 parts by weight of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Co., Ltd.) After 30 parts by weight of N, N-dimethylformamide, and stirred at 40 ° C for 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then dropped into 500 parts by weight of tap water while stirring for 1 hour to obtain a dark cyan suspension. The suspension obtained above was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60 ° C. to obtain 11.3 parts by weight of a compound of the following Chemical Formula 16 (yield: 86%).

[Chemical Formula 16]

The compound of the above formula is dissolved in chloroform 0.35g 16, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with ion-exchanged water, so that the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz Cell and optical path length; 1 cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 16 showed an absorbance of 3.1 at λmax = 630 nm.

Synthesis Example 6.

6-1.

This reaction is carried out under a nitrogen atmosphere.

33 parts by weight of potassium thiocyanate and 160 parts by weight of acetone were put into a flask having a cooling tube and a stirring device, and then stirred at room temperature for 30 minutes. Then, 50 parts by weight of 2-methylbenzidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 10 minutes.

After the dropwise addition, the mixture was stirred at normal temperature for 2 hours, and the reaction mixture was ice-cooled, and then 41.6 parts by weight of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropping, the mixture was stirred at normal temperature for 30 minutes.

Next, after the reaction mixture was ice-cooled, 34.2 parts by weight of a 30% sodium hydroxide aqueous solution was added dropwise, and the mixture was stirred at normal temperature for 30 minutes. Of course Then, 32.1 parts by weight of chloroacetic acid was added dropwise at room temperature. After the dropwise addition was completed, the mixture was stirred under reflux for 7 hours.

Next, after cooling the reaction mixture to normal temperature, 120 parts by weight of tap water and 200 parts by weight of toluene were added to the reaction solution, and the mixture was stirred for 30 minutes. Then, it was left to stand for 30 minutes, and the reaction mixture was separated into an organic layer and an aqueous layer.

After the water layer was discarded by a liquid separation operation, the organic layer was washed in the order of 200 parts by weight of 1N hydrochloric acid, 200 parts by weight of tap water, and 200 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The obtained organic layer was removed by evaporating the solvent using an evaporator, and a pale yellow liquid was obtained. The obtained pale yellow liquid was purified by column chromatography, and the purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 40.5 parts by weight (yield 41%) of the compound of the following Chemical Formula 17.

6-2.

This reaction is carried out under a nitrogen atmosphere.

In a flask having a cooling tube and a stirring device, 9.7 parts by weight of the compound of Chemical Formula 17 produced in Synthesis Example 6-1, 4, After 10 'parts by weight of 4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20 parts by weight of toluene, 14.8 parts by weight of phosphorus oxychloride was added and stirred at 95 to 100 ° C. 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then diluted with 170 parts by weight of isopropyl alcohol. Then, 300 parts by weight of saturated saline was poured into the diluted reaction solution, and then 100 parts by weight of toluene was added, followed by stirring for 30 minutes. The stirring was stopped, and the mixture was left for 30 minutes to separate the reaction solution into an organic layer and an aqueous layer.

After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts by weight of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer.

The obtained organic layer was evaporated and removed with an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 15.1 parts by weight of a compound of the following chemical formula 18 Rate 75%).

Mass Analysis of Compound of Chemical Formula 18

Ionization mode: ESI ⁺ : m / z = 615.4 [M-Cl] ⁺

Accurate mass: 650.3

6-3.

This reaction is carried out under a nitrogen atmosphere.

A flask having a cooling tube and a stirring device was charged with 10 parts by weight of the compound of Chemical Formula 18 produced in the above Synthesis Example 6-2, and 5.7 weight of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.). Parts and 30 parts by weight of N, N-dimethylformamide were stirred at 40 ° C for 3 hours.

Next, the reaction mixture was cooled to normal temperature, and then dropped into 500 parts by weight of tap water while stirring for 1 hour to obtain a dark cyan suspension. The suspension obtained above was filtered to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60 ° C to obtain 13.2 parts by weight (yield 96%) of the compound of the following Chemical Formula 19.

The compound of the above formula is dissolved in chloroform 0.35g 19, so that the volume becomes 250cm ^3, in which the 2cm ³ was diluted with ion-exchanged water, so that the volume becomes 100cm ³ (concentration: 0.028g / L), using a spectrophotometer (quartz Cell and optical path length; 1 cm) The absorption spectrum was measured.

The compound of the above Chemical Formula 13 showed an absorbance of 2.7 at λmax = 627 nm.

Production Example 1. Production of Pigment Dispersion

15: 6 to 12 parts by weight of CI Pigment Blue as a pigment, 4 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate as a solvent, and propylene glycol methyl ether 40 parts by weight were mixed and dispersed with a bead mill for 12 hours to produce a pigment dispersion liquid M1.

<Production of cyan photosensitive resin composition>

Examples 1 to 10 and Comparative Examples 1 to 8.

The cyan photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were produced in accordance with the compositions of Table 1 below.

Cyan colorant (A)

A-1: Compound of Chemical Formula 10 produced in Synthesis Example 2

A-2: Compound of Chemical Formula 12 produced in Synthesis Example 3

A-3: Compound of Chemical Formula 13 produced in Synthesis Example 4

A-4: Compound of Chemical Formula 16 produced in Synthesis Example 5

A-5: Compound of Chemical Formula 19 produced in Synthesis Example 6

M1: Pigment dispersion liquid produced in Production Example 1

Alkali-soluble resin (B): Alkali-soluble resin produced in Synthesis Example 1

Photopolymerizable compound (C): KAYARAD DPHA (manufactured by Nippon Kayaku)

Photopolymerization initiator (D)

D-1: UPI-22 (made by Daito Corporation)

D-2: OXE-01 (manufactured by BASF)

Solvent (E)

E-1: Propylene glycol monomethyl ether acetate

E-2: Propylene glycol monomethyl ether

Additive (F)

Antioxidant: Irganox1035 (manufactured by BASF)

Experimental example 1. Manufacturing and characteristic evaluation of color filters

The cyan photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were applied to a 2-inch glass substrate (EAGLE XG) by a spin coating method, and then placed on a hot plate at a temperature of 100 ° C. It was maintained for 3 minutes, and a thin film was formed. Then, a test photomask having a line / gap pattern of 1 to 100 μm was placed on the film, the distance from the test photomask was 300 μm, and ultraviolet rays were irradiated. At this time, all 1 kW high-pressure mercury lamps including g, h, and i lines were used, and ultraviolet rays were irradiated at 60 mJ / cm ² without using a special optical filter.

The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution at pH 10.5 for 2 minutes to develop. Then, the glass plate coated with the film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C. for 25 minutes to manufacture each color filter. The film thickness of the color filter manufactured as described above was 2.4 μm.

1. Measurement of transmittance

The color filter was manufactured by the method described above, and the color filter was manufactured without using a test photomask. The transmittance was measured using a colorimeter (manufactured by Olympus Corporation, OSP-200). The results are shown in Table 2 below.

2. Determination of adhesion

The pattern of the color filter manufactured as described above was observed with an optical microscope, and the degree of the small defect phenomenon in the pattern was evaluated. Table 2 below shows the evaluation criteria as described below.

<Evaluation criteria>

○: No small defects on the pattern

△: 1 to 3 small defects on the pattern

×: 4 or more small defects in the pattern

3. Determination of residual film rate

After applying the cyan photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 to a substrate using a spin coater, they were prebake at 100 ° C for 1 minute, and then exposed at 365 nm at 230 Post-bake was performed at 20 ° C for 20 minutes, and the thickness ratio (%) of the resist film before and after post-baking was measured. The evaluation results are shown below, and the results are shown in Table 2 below.

From the results of Table 2 described above, Examples 1 to 10, which are the cyan photosensitive resin composition of the present invention, show results that are excellent in transmittance, adhesion, and chemical resistance. More specifically, the cyan photosensitive resin composition of Examples 6 to 10 using the cyan dye and cyan pigment of the above Chemical Formula 1 as a cyan colorant and Example 1 using only the cyan dye of the above Chemical Formula 1 as a cyan colorant. The cyan photosensitive resin composition of ~ 5 exhibited excellent results in terms of adhesion and chemical resistance.

In contrast, the cyan photosensitive resin composition of Comparative Examples 1 to 5 in which the compound of the above Chemical Formula 2 was not used as the photopolymerization initiator was poor in adhesiveness and residual film rate.

In addition, the cyan photosensitive resin composition of Comparative Example 6 in which the dye of the above Chemical Formula 1 was not used and the pigment was used showed a result of slightly inferior transmittance, adhesion, and residual film rate. The pigment was used, and the dye of the above Chemical Formula 1 was not used. The cyan photosensitive resin composition of Comparative Example 7 with the photopolymerization initiator of the above Chemical Formula 2 showed poor adhesion and residual film rate.

The cyan photosensitive resin composition of Comparative Example 8 in which the dye of the above Chemical Formula 1 was used, no pigment was used, and the photopolymerization initiator of the above Chemical Formula 2 was not used showed poor adhesion and residual film rate.

Therefore, the cyan photosensitive resin composition of the present invention can be confirmed to have excellent transmittance, adhesion, and residual film ratio, particularly excellent adhesion, and there is no reduction in sensitivity caused by the dye, which can solve the problem of peeling the pattern in the development process. problem.

Claims (7)

A cyan photosensitive resin composition is a cyan photosensitive resin composition comprising a cyan colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the cyan colorant contains the following: The dye of Chemical Formula 1, wherein the photopolymerization initiator includes a compound of Chemical Formula 2 below,

Each of the above R ₁ to R _{6 is the} same or different, and is hydrogen, an aryl group having 6 to 12 carbon atoms with or without a substituent, or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be Oxygen is contained between the methylene groups, and the hydrogen of the alkyl group having 1 to 20 carbon atoms may be substituted by a halogen atom or an amine group. The R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ may be respectively The groups R ₇ to R ₁₄ are the same or different, and are each a hydrogen, a halogen atom, a nitro group, a sulfofluorenyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. The group may include oxygen between methylene groups, the above R ₁₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 12 carbon atoms with or without a substituent, and the X is oxygen, sulfur, Or an amine group, where Y is a counter anion, and m is an oxidation number of Y,

The a and b are 0 or 1. When the a is 1, the b is 1. When the a is 0, the b is 0 or 1. When the a = 0 and b = 0, the R ₁₆ is hydrogen. , A halogen atom, a nitro group, a sulfonyloxy group containing a C1-C8 alkyl group which may be substituted or unsubstituted by a halogen atom, a phenylsulfonyloxy group with or without a substituent, a halogen atom Sulfonyl groups of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, heterocyclic sulfonyl groups having 7 to 20 carbon atoms having or not having a substituent, or 7 to 6 carbon atoms having or not having a substituent 20 fused ring sulfofluorenyl group, (2) in the case of a = 0 and b = 1, the above R ₁₆ is a phenyl group with or without a substituent, and a carbon number of 7 or more with or without a substituent A heterocyclic group of 20 or a fused ring group having 7 to 20 carbon atoms with or without a substituent. (3) In the case of a = 1 and b = 1, the above-mentioned R ₁₆ is substituted with a halogen atom or The unsubstituted sulfonyloxy group of an alkyl group having 1 to 8 carbon atoms, or the phenylsulfonyloxy group containing or not having a substituent, the above-mentioned R ₁₇ and R ₁₈ are each the same or different, and are hydrogen and a carbon number of 1 to 22 alkyl group, 1 to 10 carbon group containing halogen atom, and ether at the end A thioether group or a C 1 to 15 alkyl group, with or without a substituted phenyl group, or a phenyl group having 7 to C 11, said R ₁₇ and R ₁₈ may form a ring, R ₁₉ is the above-described The following Chemical Formula 3 or Chemical Formula 4,

Each of the above R ₂₀ and R _{22 is the} same or different, and is an alkyl group having 1 to 17 carbon atoms, an alkyl group having 2 to 5 carbon atoms including a halogen atom, and an alkyl group having 2 to 7 carbon atoms at the end of which is an ether group or a thioether group. Group, phenyl group with or without substituents, phenylalkyl group with 7 to 11 carbon atoms with or without substituents, phenoxyalkyl group with 7 to 10 carbon atoms with or without substituents, containing Or a heterocyclic group having 7 to 20 carbons without a substituent or a fused ring group having 7 to 20 carbons with or without a substituent, wherein R ₂₁ is an alkyl group with 1 to 17 carbons, and contains halogen 1 to 7 carbon atoms of the atom, 2 to 7 carbon atoms of the ether or thioether group at the terminal, 2 to 4 carbon atoms of the amino group containing or not having a substituent, or not Substituted phenyl, 7 to 11 carbon phenyl alkyl group with or without substituents, 7 to 10 carbon phenyl alkyl group with or without ether at the end Group, a fused ring group having 7 to 20 carbon atoms with or without a substituent, or a heterocyclic group having 7 to 20 carbon atoms with or without a substituent, the above-mentioned R ₂₃ is an alkyl group with 1 to 16 carbon atoms 1 to 6 carbons containing a halogen atom, with or without substituents Group, phenylalkyl group with 7 to 10 carbon atoms with or without substituents, phenylalkyl group with 7 to 9 carbon atoms with or without substituents at the end, with or without Condensed ring group having 7 to 20 carbon atoms with a substituent, or heterocyclic group having 7 to 20 carbon atoms with or without a substituent. The cyan photosensitive resin composition according to claim 1, wherein the cyan colorant additionally contains a pigment. The cyan photosensitive resin composition according to claim 2, wherein the pigment comprises one or more selected from C.I. Pigment Blue 15: 6 and C.I. Pigment Violet 23. The cyan photosensitive resin composition according to claim 1, wherein [Y] ^m- in Chemical Formula 1 is selected from an anion of a heteropolyacid containing tungsten, an anion of a homopolyacid containing tungsten, an anion of phosphotungstic acid, One of an anion of silicotungstic acid and an anion of polytungstic acid. The cyan photosensitive resin composition according to claim 1, comprising 5 to 60% by weight of a cyan colorant, 10 to 80% by weight of an alkali-soluble resin, and light based on the total weight of the solid content in the cyan photosensitive resin composition. The polymerizable compound is 5 to 50% by weight and the photopolymerization initiator is 0.1 to 40% by weight, and the solvent contains 60 to 90% by weight based on the total weight of the cyan photosensitive resin composition. The cyan color filter manufactured using the cyan photosensitive resin composition as described in any one of claims 1 to 5 is used. A display device includes the cyan color filter as claimed in claim 6.