KR102186496B1 - Colored photosensitive resin composition - Google Patents

Abstract

The present invention comprises a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the colorant (A) is a compound represented by Formula 1, and And at least one selected from pigments and dyes; The solvent (E) is a colored photosensitive resin composition comprising a solvent having a boiling point of 100 to 169 °C and a solvent having a boiling point of 170 to 250 °C, a color filter manufactured using the same, and an image including the color filter It relates to a display device.

Description

Colored photosensitive resin composition TECHNICAL FIELD

The present invention relates to a colored photosensitive resin composition, a colored pattern formed from the resin composition, a color filter including the colored pattern, and an image display device having the same.

Color filters are widely used in various display devices, such as image pickup devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. Color filters used in the image pickup device and liquid crystal display device are composed of three colored patterns of red, green, and blue, or are yellow, magenta, and cyan ( Cyan) consists of three color coloring patterns.

The colored pattern of each of the color filters is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

In recent years, various display devices including solid-state imaging devices such as digital cameras, and color filters for liquid crystal display devices (LCDs) are required to have high luminance and high colorability in order to improve processability and quality.

Meanwhile, Korean Patent Publication No. 2013-0134494 discloses C.I Pigment Green 7 and C.I. Although a resin composition using Pigment Yellow 185 is disclosed, there is a problem that high luminance and high colorability are not satisfied at the same time.

Republic of Korea Patent Publication No. 2013-0134494

The present invention, as devised to solve the problem of the prior art,

It is an object of the present invention to provide a colored photosensitive resin composition that is excellent in luminance and colorability, has high sensitivity, and has a low incidence of defects such as foreign matter.

In addition, an object of the present invention is to provide a color filter including the colored photosensitive resin composition and an image display device including the same.

The present invention,

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),

The colorant (A) includes a compound represented by the following formula (1), and at least one selected from pigments and dyes;

The solvent (E) provides a colored photosensitive resin composition comprising a solvent having a boiling point of 100 to 169 °C and a solvent having a boiling point of 170 to 250 °C.

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

In addition, the present invention

It provides a color filter including a pattern formed of the colored photosensitive resin composition.

In addition, the present invention

It provides an image display device including the color filter.

The colored photosensitive resin composition of the present invention is excellent in luminance and colorability, and can provide an effect of low incidence of defects such as foreign matter.

1 is a graph showing the transmission spectrum of each colorant.

The present invention,

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),

The colorant (A) includes a compound represented by the following formula (1), and at least one selected from pigments and dyes;

The solvent (E) provides a colored photosensitive resin composition comprising a solvent having a boiling point of 100 to 169°C and a solvent having a boiling point of 170 to 250°C.

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br.

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described. However, the present invention is not limited to these components.

(A) colorant

The colorant (A) according to the present invention is a component capable of expressing colors such as red, green, or blue so that a pattern having a desired color can be prepared.

Pigment( a1 )

The colorant (A) contained in the colored photosensitive resin composition of the present invention is characterized in that it contains a compound represented by the following formula (1) as the pigment (a1). The compound represented by Formula 1 below has a structure of ZnPc (Zinc Phthalocyanine). When the colorant (A) of the present invention contains a compound represented by the following formula (1) There is an advantage of high color reproduction.

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br;

More preferably 1 to 6 are H, 0 to 5 are Cl, and 7 to 13 are Br;

More preferably, 2 to 5 may be H, 0 to 3 may be Cl, and 8 to 13 may be Br. In this case, it is preferable in that the effect of the present invention is further maximized.

C.I. Pigment Green 58 (G58) has the advantage of high luminance, but the content of pigment increases in order to realize high colorability.If the composition contains a lot of pigment, developability decreases and the pattern formed by the composition is at risk of peeling off. There is a problem that the sensitivity is lowered may occur.

However, in the present invention, by using the pigment represented by Formula 1 as a colorant, it is possible to design a resist with high color reproduction even if the content of the pigment is small.

On the other hand, when CI Pigment Green 7 (G7) is included in the resin composition, it can exhibit high colorability even when the pigment content is reduced, so that it is advantageous in use, but there is a problem of low luminance. However, the compound of Formula 1 contained in the colored photosensitive resin composition of the present invention functions as a pigment to exhibit a transmission spectrum and color coordinates similar to those of CI Pigment Green 7 while being included in the colored photosensitive resin composition to exhibit excellent luminance. As can be seen in FIG. 1, the compound of Formula 1 has a transmission spectrum at a wavelength of 400 nm to 610 nm similar to CI Pigment Green 7.

In the present specification, Tmax refers to the wavelength at which the transmittance of the pigment is at the maximum, and T _50% refers to the wavelength at which the transmittance of the pigment is 50% or more of the maximum value.

In one embodiment of the present invention, the Tmax of the compound represented by Formula 1 may be 500 to 530nm, and in this case, it is preferable in terms of excellent colorability.

In addition, as another embodiment of the present invention, T _{50 %} of the compound represented by Formula 1 may be 445 to 580 nm, and in this case, it is preferable in terms of excellent colorability.

The compound of Formula 1 is preferably contained in an amount of 0.05 to 30% by weight based on the total weight of the colored photosensitive resin composition of the present invention, more preferably 0.05 to 25% by weight, and contained in 0.05 to 20% by weight. It is more preferable. When the compound of Formula 1 is included in the range of 0.05 to 30% by weight based on the above, it is preferable because it can express a high-brightness resist while having excellent colorability.

The colorant (A) according to the present invention is a component capable of expressing colors such as red, green, or blue so that a pattern having a desired color can be prepared, in addition to the compound of Formula 1, and a pigment commonly used in the art and Characterized in that it comprises at least one selected from the group consisting of dyes, it can be prepared in the form of a mill base.

The compound represented by Formula 1, and at least one selected from pigments and dyes, is preferably 1: 0.050 to 1: 18.0, more preferably 1: 0.1 to 1: 9, even more preferably 1: 0.2 to It is recommended to be included in a weight ratio of 1: 4. When included in the above weight ratio, it has advantages of high coloration and high luminance, and it is preferable because it has advantages of improved process margin and excellent sensitivity.

In this case, the colorant including the compound of Formula 1 according to the present invention as a pigment may have a color coordinate of x=0.1 to 0.35 when y=0.6 or more in the XYZ color system.

The pigment (a1) includes an organic pigment and an inorganic pigment, and these may be used alone or in combination of two or more. It may be more preferable to use an organic pigment in terms of excellent heat resistance and color development. The organic pigment may be a synthetic colorant or a natural colorant.

If necessary, the organic pigment is rosin treated; Surface treatment using a pigment derivative into which an acidic group or a basic group is introduced; Graft treatment on the surface of a pigment using a polymer compound or the like; Fine particle treatment by a sulfuric acid fine particle method or the like; Or a washing treatment with an organic solvent or water to remove impurities; It may have been.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, inorganic salts of barium sulfate (extender pigment), and the like. More specifically, the metal compounds include iron, cobalt, aluminum, cadmium, lead, copper, and titanium. , Oxides of metals such as magnesium, chromium, zinc, antimony, and carbon black, or complex metal oxides.

As a specific example of the pigment (a1), more preferably, a compound classified as a pigment in the Color Index (Publisher: The Society of Dyers and Colourists) may be mentioned, and more specifically, the following color index ( CI) Pigments exemplified by number may be mentioned, but the present invention is not limited thereto, and at least one selected from them may be used by co-dispersing using a binder resin, a dispersant, or the like so as to suit the desired color.

Specific examples of CI pigment yellow include CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117 , 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214, and the like;

Specific examples of the CI pigment orange include CI pigment orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

Specific examples of CI Pigment Red include CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254 , 255, 264, and 265;

Specific examples of CI Pigment Blue include CI Pigment Blue 15:3, 15:4, 15:6, 16, 22, 28, 60, and the like;

Specific examples of the CI pigment violet include CI pigment violet 14, 19, 23, 29, 32, 177, and the like,

As a specific example of CI pigment green, CI pigment green 7, 36, 58, etc. are mentioned.

Among the pigments exemplified above, preferably, it may be more preferable to contain at least one selected from the group consisting of CI pigment yellow 138, CI pigment yellow 129, CI pigment yellow 150, and CI pigment yellow 185. have.

dyes( a2 )

The colorant (A) of the present invention may further contain a dye (a2). The dye may be used without limitation as long as it has solubility in an organic solvent or is dispersible. It is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, heat resistance, and solvent resistance. In the case of a dye that is not soluble in an organic solvent, it is also possible to disperse and use.

As the dye (a2), one or more selected from acidic dyes having an acidic group such as sulfonic acid or carboxylic acid, salts of acidic dyes and nitrogen-containing compounds, sulfonamides of acidic dyes, and derivatives thereof may be used. In addition, it is also possible to select from azo-based, xanthene-based, phthalocyanine-based acid dyes and derivatives thereof.

As the dye (a2), preferably, a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in the dye note (color dyeing company) can be mentioned.

Specific examples of the dye (a2),

C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135;

C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent orange 63;

C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91:1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197;

C.I. Solvent Violet No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59;

C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent blue 70;

CI Solvent Green No. 3, CI Solvent Green No. 5, CI Solvent Green No. 7, and the like, but are not limited thereto.

The colorant (A) may be included in a weight fraction of preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the solid content in the colored photosensitive resin composition. If the content of the colorant (A) is less than 5% by weight, the color separation ability of the formed pattern may be reduced, and if it exceeds 70% by weight, lithography performance may be degraded, resulting in problems such as residues or undeveloped.

In the present invention, the solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

(B) binder resin

The binder resin (B) contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to the alkaline developer used in the developing step. In the present invention, the binder resin is not particularly limited, but it is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The monomer having a carboxyl group is not particularly limited, and specific examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth)acrylate, and the like, and acrylic acid and methacrylic acid are more preferable. These can be used by selecting one or more.

The other copolymerizable monomer is not particularly limited as long as it is a monomer having a carbon-carbon unsaturated bond, and specific examples include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkylcarboxylate compounds such as aminoethylacrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. And unsaturated oxetane carboxylate compounds. These monomers may be used alone or in combination of two or more.

According to the present invention, the molecular weight distribution of the binder resin (B), that is, the weight average molecular weight (weight average molecular weight (Mw) / number average molecular weight (Mn)) relative to the number average molecular weight is preferably 1.5 to 6.0, more preferably It is good in terms of developability to be 1.8 to 4.0.

The acid value of the binder resin (B) is preferably 30 to 170 mgKOH/g based on solid content, and more preferably 50 to 150 mgKOH/g. When the acid value of the binder resin (B) is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development rate, and when the acid value exceeds 170 mgKOH/g, the adhesion to the substrate is reduced and the pattern is short-circuited. This is apt to occur, and a problem arises in compatibility with the colorant, the colorant in the colored photosensitive resin composition is precipitated, or the storage stability of the colored photosensitive resin composition is lowered, so that the viscosity may increase, which is not preferable.

The binder resin (B) is preferably contained in an amount of 5 to 85% by weight, more preferably 10 to 70% by weight based on the solid content in the colored photosensitive resin composition of the present invention. When the content of the binder resin (B) is 5 to 85% by weight based on the above, the solubility in the developer is sufficient, so that the development residue is difficult to occur on the substrate in the non-pixel portion, and the film in the pixel portion of the exposed portion during development It is preferable because reduction is prevented and the omission of non-pixel portions tends to be good.

(C) Photopolymerization compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator (D) described later by light irradiation, and is polymerized by the action of a photopolymerization initiator. It does not specifically limit if it is a possible compound. Preferably, a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher polyfunctional monomer may be used, and one or more monomers selected therefrom may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpi Rolidone, etc., and commercially available products include Aronics M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku), or Biscotti 158 (Osaka Yuki Kagaku High School), but are limited thereto. It is not.

Specific examples of the bifunctional monomer include 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylic Rate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, propylene glycol dimethacrylate, urethane(meth)acrylate Examples of commercially available products include Aaronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscote 260 (Osaka Yuki Kagaku High School), AH-600, AT- 600 or UA-306H (Kyoeisha Chemical Co., Ltd.) may be mentioned, but is not limited thereto.

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta(meth)acrylate, ethoxyl Rated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., and commercially available products include Aronics M -309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), and the like, but is not limited thereto.

Of the photopolymerizable compounds exemplified above, it is more preferable to use a trifunctional or higher polyfunctional monomer, and (meth)acrylates and urethane (meth)acrylates have excellent polymerizability and can improve strength. desirable.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 45% by weight, more preferably 10 to 35% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound (C) is in the range of 5 to 45% by weight based on the above, it is preferable because the strength and smoothness of the pixel portion become good.

(D) Light polymerization Initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention can initiate polymerization of the above-described photopolymerizable compound (C) by exposure to radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron rays, and X-rays. It is a compound that generates radicals and the like.

The photopolymerization initiator is commonly used in the art within a range that does not impair the object of the present invention, and the type of the photopolymerization initiator is not particularly limited as long as it can polymerize the binder resin and the photopolymerizable compound. Representative examples include, but are limited to, oxime compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, biimidazole compounds, triazine compounds, thioxanthone compounds, and anthracene compounds. It is not, and one or more can be selected and used from this. Among these, it may be more preferable to use an oxime-based compound in consideration of polymerization characteristics, initiation efficiency, and absorption wavelength.

As the oxime compound, for example, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z)-2-((benzoyloxy)imino)-1-(4- (Phenylthio)phenyl)octan-1-one, (E)-1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidine)amino )Oxy)ethanone and (E)-1-(((1-(6-(4-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-2-methylbenzoyl) )-9-ethyl-9H-carbazol-3-yl)ethylidine)amino)oxy)ethanone, etc., and commercially available products include BASF's OXE-01 and OXE-02, but are limited thereto. It does not become.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and the like.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the biimidazole-based compound 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'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or imidazole compounds in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group. Among these, more preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole or 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole And the like.

As the triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-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)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

As the thioxanthone compound, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. Can be mentioned.

The content of the photopolymerization initiator (D) is not particularly limited, but is preferably contained in an amount of 0.1 to 40% by weight based on the total weight of the solids in the binder resin (B) and the photopolymerizable compound (C), and 1 to 30% by weight It is more preferable to be included in %. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition is highly sensitive and thus the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, the strength of the pixel portion formed by using the colored photosensitive resin composition of the present invention and smoothness on the surface of the pixel portion can be improved, which is preferable.

As other specific examples, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, campoquinone, phenylclioxyl Acid methyl, titanocene compounds, and the like.

Meanwhile, according to an embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiator auxiliary agent (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation aid, so that the sensitivity is further increased and the productivity can be improved.

As the photopolymerization initiation aid (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl) Rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. I can.

(E) solvent

The solvent (E) according to the present invention serves to dissolve other components included in the colored photosensitive resin composition, has a boiling point of 100 to 250° C., and a solvent commonly used in the field may be used without particular limitation. The solvent (E) may preferably be used by selecting one or more from ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides, but is not limited thereto.

In the present invention, the solvent (E) is characterized in that it includes a solvent having a boiling point of 100 to 169 °C and a solvent having a boiling point of 170 to 250 °C.

When a solvent having a boiling point of 100 to 169°C is used alone, the drying speed is high, and thus foreign matters may be generated in the nozzle during the manufacturing process of the color filter, which may cause defects. On the other hand, when a solvent having a boiling point of 170 to 250°C is used alone, the tack-time for each process may be lengthened.

As a specific example of the solvent having a boiling point of 100 to 169°C, propylene glycol methyl ether acetate, ethyl lactate, 2-amino-2-methyl-1,3-propanediol, ethyl-3-ethoxypropionate, propylene Glycol n-propyl ether, methyl 3-methoxypropionate, and the like, but are not limited thereto, and one or more may be selected and used therefrom.

The solvent having a boiling point of 100 to 169°C is preferably contained in an amount of 30 to 95% by weight, more preferably 50 to 90% by weight, based on the total weight of the solvent (E).

As specific examples of the solvent having a boiling point of 170 to 250° C., ethyl-3-ethoxypropionate, gamma butyrolactone, 1,3-butylene glycol diacetate, diethylene glycol methyl ethyl ether, diethylene glycol mono Ethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate and diethylene glycol monoethyl ether Acetate and the like may be mentioned, but the present invention is not limited thereto, and one or more may be selected and used therefrom.

The solvent having a boiling point of 170 to 250° C. is preferably contained in an amount of 5 to 70% by weight, more preferably 5 to 50% by weight, based on the total weight of the solvent (E).

In addition, as a solvent having a boiling point in the range of 100 to 250°C, specifically 2-amino-2-ethyl-1,3-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc. Can be mentioned.

Among the above, it may be more preferable to use diethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, or diethylene glycol monobutyl ether acetate.

In addition, in the present invention, the viscosity of the colored photosensitive resin composition containing the solvent (E) is preferably 2 to 20 mPa·s based on 25°C, more preferably 2 to 15 mPa·s, and 2 to 5 It may be more preferable to be mPa·s. When the viscosity of the solvent is 2 to 20 mPa·s, there is an advantage in that there is little occurrence of foreign substances, and thus the process margin is excellent.

The content of the solvent (E) contained in the colored photosensitive resin composition of the present invention is preferably contained in 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention. Can be included as When the solvent (E) is included within the above-described range, the coating property becomes good when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. It can provide an effect.

(F) additive

In addition to the above components, the colored photosensitive resin composition of the present invention includes additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, anti-aggregation agents, and pigment dispersants as required by those skilled in the art within a range that does not harm the object of the present invention (F) may be further included.

As a specific example of the other polymer compound, a curable resin such as an epoxy resin or a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. However, it is not limited thereto.

The curing agent is used to increase deep curing and mechanical strength, and specific examples thereof include, but are not limited to, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

As a specific example of the epoxy compound, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxidation, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexane dicarboxylic acid bisoxetane, but are limited thereto. It does not become.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Specifically, as the curing auxiliary compound, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators may be used. The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. As the commercially available epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries, Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) (Manufactured by Shin-Japan Ewha Corporation), and the like.

The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and as a specific example of the surfactant, a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the fluorine-based surfactant are commercially available products, such as Megapieces F-470, F-471, F-475, F-482, F-489, etc. manufactured by Dai Nippon Ink Chemicals.

Examples of the silicone surfactant are commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicon, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF- 4460 and TSF-4452.

Each of the above-exemplified surfactants may be used alone or in combination of two or more.

As specific examples of the adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl At least one selected from trimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane may be used.

The adhesion promoter may be included in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, based on the solid content in the colored photosensitive resin composition of the present invention.

As a specific example of the antioxidant, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)prop Foxy]- 2,4,8,10 -tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine, 3,9-bis[2-{3-(3-tert) -Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5- Methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''- Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert) -Butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis(4-methyl-6-t-butylphenol), 2 ,6-di-t-butyl-4-methylphenol, and the like, but are not limited thereto.

Specific examples of the anti-aggregation agent include sodium polyacrylate, but are not limited thereto.

The pigment dispersant is a component that can be added for deagglomeration and stability maintenance of the pigment (a1). As an example of a method for uniformly dispersing the particle diameter of the pigment (a1), there is a method of dispersing by adding a pigment dispersant, and through this, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant generally used in the art may be used without limitation. Preferably, an acrylate-based dispersant (hereinafter also referred to as “acrylic dispersant”) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and DISPER BYK LPN-6919. Each of the acrylic dispersants exemplified above may be used alone or in combination of two or more.

In addition to the above-described acrylate-based dispersant, the pigment dispersant may use other resin type pigment dispersants. The other resin type pigment dispersants include known resin type pigment dispersants, especially polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free An oily pigment dispersant such as an amide formed by reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine) or a salt thereof; Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; And phosphate esters and adducts of ethylene oxide/propylene oxide.

As a commercial item of the above resin type pigment dispersant, for example, the brand names of BYK-Chemi: 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's brand names: 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; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like.

The pigment dispersant is preferably included in an amount of 5 to 60 parts by weight, more preferably 5 to 40 parts by weight based on 100 parts by weight of the solid content of the pigment (a1) used. If the content of the pigment dispersant is less than 5 parts by weight based on the above, it is difficult to atomize the pigment, or it may cause problems such as gelation after dispersion, and if it exceeds 60 parts by weight, the viscosity may increase, which is not preferable. .

The method for preparing the colored photosensitive resin composition of the present invention will be described as follows.

First, the pigment (a1) of the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a pigment dispersant, part or all of the binder resin (B), or a dye (a2) may be mixed together with a solvent (E) to dissolve or disperse.

To the mixed dispersion, add the dye (a2), the remainder of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), and optionally additives (F) and solvents (E) to a predetermined concentration. It can be added to prepare a colored photosensitive resin composition according to the present invention.

Further, the present invention includes a colored pattern made of the colored photosensitive resin composition. The colored pattern may be prepared by applying the colored photosensitive resin composition of the present invention on a substrate, photocuring, and developing. The thickness of the colored pattern is not particularly limited, and may be, for example, 1 to 6 μm.

The colored pattern may be formed, for example, in the following manner.

First, the colored photosensitive resin composition is applied onto a substrate or a layer consisting of a solid content of the previously formed photosensitive resin composition, and prebaked from the applied photosensitive resin composition layer to remove volatile components such as a solvent to obtain a smooth coating film.

As the coating method, for example, spin coating, cast coating, roll coating, slit and spin coating, or slit coating can be performed.

After the above application, a colored photosensitive resin composition layer is formed by heating after prebaking (heat drying) or drying under reduced pressure to evaporate volatile components such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C.

The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel light rays are uniformly irradiated to the entire exposed portion and accurate positioning of the mask and the substrate is performed.

Further, after that, the cured coating film is brought into contact with an alkali developer to dissolve and develop the non-exposed portion, whereby a desired pattern shape can be obtained. As the developing method, a liquid addition method, a dipping method, a spray method, or the like may be performed, and the substrate may be tilted at an arbitrary angle during development.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and/or organic alkaline compounds.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, carbonic acid. Potassium, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds may be used alone or in combination of two or more.

The concentration of the alkaline compound in the alkali developer is, for example, 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, and sorbitan fatty acids. Ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; Alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; And the like.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride; Quaternary ammonium salt; And the like.

These surfactants can be used alone or in combination of two or more.

The concentration of the surfactant in the alkaline developer is, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After the above development, washing with water may be performed, and post-baking for 10 to 60 minutes at 150 to 230° C. may be performed as needed.

<Color filter>

In addition, the present invention provides a color filter including a colored pattern made of the colored photosensitive resin composition. The color filter of the present invention includes a substrate and a colored pattern made of the colored photosensitive resin composition of the present invention on the substrate. The substrate is a transparent material, and a material having sufficient strength and support for stability of the color filter may be used. Preferably, glass having excellent chemical stability and high strength can be used.

As a method of manufacturing the color filter, a conventional method well known in the art may be used.

<Image display device>

Further, the present invention provides an image display device including the color filter. Specific examples of the image display device include a liquid crystal display (liquid crystal display; LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, and a display for a digital camera. A display device such as a device and a display device for car navigation. In particular, a color display device is suitable.

The image display device includes a configuration known to a person skilled in the art, except that the color filter is provided, that is, the present invention includes an image display device to which the color filter of the present invention can be applied. .

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes can be made within the scope of the present invention. The scope of the present invention will be determined by the technical idea of the claims to be described later.

In addition, "%" and "parts" indicating the content in the following Preparation Examples, Examples, and Comparative Examples are based on weight unless otherwise noted.

Preparation of colored photosensitive resin composition

A colored photosensitive resin composition having the composition and content shown in Table 1 was prepared.

(Part by weight) division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Colorant (A) A-1 3.07 3.07 - - 3.07 3.07 A-2 - - 3.07 3.07 - - A-3 2.6 2.6 2.6 2.6 2.6 2.6 Binder resin (B) B-1 4.1 4.1 4.1 4.1 4.1 4.1 Photopolymerization
Compound (C) C-1 2.8 2.8 2.8 2.8 2.8 2.8 Light polymerization
Initiator (D) D-1 1.2 1.2 1.2 1.2 1.2 1.2 Solvent (E) E-1 70 70 70 85 85 - E-2 15 - 15 - - 85 E-3 - 15 - - - Additive (F) F-1 0.05 0.05 0.05 0.05 0.05 0.05 F-2 1.17 1.17 1.17 1.17 1.17 1.17 F-3 0.01 0.01 0.01 0.01 0.01 0.01 A-1: In the structure of Formula 1, A ¹ to A ¹⁶ are H: 5, Cl: 2, Br: 9 (manufacturer: DIC) (Tmax: 515 nm, T _{50 %} : 450 to 575 nm)
A-2: G7 (in the structure of Formula 1, the central atom is Cu, and A ¹ to A ¹⁶ are Cl: 14 to 16, H: 0 to 2 mixture)
A-3: Y129 (manufacturer: DIC)

B-1: Methacrylic acid: benzyl methacrylate = 31:69 (molar ratio), weight average molecular weight = 30,000, acid value = 105 mgKOH/g of methacrylic acid and benzyl methacrylate copolymer

C-1: Dipentaerythritol hexaacrylate (KAYARAD DPHA; Manufacturer: Nippon Kayaku Co., Ltd.)

D-1: OXE-02 (manufacturer: Ciba)

E-1: Propylene glycol monomethyl ether acetate (boiling point 146°C)
E-2: 1,3-butylene glycol diacetate (boiling point 232°C)
E-3: ethyl-3-ethoxypropionate (boiling point 170°C)

F-1: Silicone surfactant (SH-8400)
F-2: Acrylic pigment dispersant (DISPER BYK-2001, manufactured by BYK)
F-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

< Manufacturing example > Manufacturing of color filters

A color filter was manufactured using the colored photosensitive resin composition prepared in Examples 1 to 2 and Comparative Examples 1 to 4.

Each of the above colored photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in a stepwise shape in the range of 1 to 100% and a line/space pattern of 1 µm to 50 µm was placed on the thin film, and the interval with the test photo mask was set to 100 µm. Was investigated. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm ² using a 1KW high-pressure mercury lamp containing all g, h, and i lines, and no special optical filter was used. The UV-irradiated thin film was developed by immersing it in a developing solution of a KOH solution having a pH of 10.5 for 2 minutes. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

< Experimental example > Evaluation of colored photosensitive resin composition

Experimental example 1. Luminance measurement

The luminance was measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 2 below.

Experimental example 2. Chromaticity ( Color coordinates ) Measure

The color coordinates of the colored layer were measured using a microscopic spectrometer OSP-SP2000, and the results are shown in Table 2 below.

Experimental example 3. Dryness evaluation

1 mL of each of the colored photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 4 was added dropwise on the glass substrate, and after standing for 3 min, the substrate was erected to check whether the photosensitive resin composition flowed. According to whether or not the photosensitive resin composition flows, it is divided into ○ and X, and is shown in Table 2 below.

<Drying evaluation criteria>

Flow within 1 min: ○

No flow within 1 min (bad tack-time): X

Experimental example 4. Viscosity evaluation

The viscosity of the colored photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 4, which was installed in a thermostat at 25°C and heated to 25°C, was measured, and the viscosity thereof is shown in Table 2 below.

<Viscosity evaluation criteria>

At 25°C,

Less than 2 to 5 mPa·s: excellent

5 to 20 mPa·s: good

Less than 2 or more than 20 mPa·s: Poor

Dryness evaluation Color coordinates (Gx, Gy) Luminance Viscosity evaluation (mPa·s) Example 1 O (0.262, 0.650) O 3.5 Example 2 O O 3.2 Comparative Example 1 O X 3.55 Comparative Example 2 X X 3.15 Comparative Example 3 X O 3.1 Comparative Example 4 X O 5

As can be seen from the results of Table 2, based on the same color coordinates, the color filters formed of the colored photosensitive resin compositions of Examples 1 to 2 belonging to the scope of the present invention exhibited excellent luminance, and dryness evaluation and viscosity evaluation Also obtained excellent results.

On the other hand, as can be seen from the results of Comparative Examples 1 to 3, in the case of the comparative example, it can be confirmed that high luminance was not expressed, or a poor result in dryness and viscosity evaluation, or a poor level compared to the examples. In addition, in the case of Comparative Example 4, it can be confirmed that the viscosity is high and the drying speed is too slow, causing a problem of increasing the tack-time, which is not preferable.

Claims (14)

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),
The colorant (A) includes a compound represented by the following Formula 1, and at least one selected from a pigment and a dye;
The solvent (E) includes a solvent having a boiling point of 100 to 169 °C and a solvent having a boiling point of 170 to 250 °C;
The solvent having a boiling point of 170 to 250° C. is ethyl-3-ethoxypropionate, gamma butyrolactone, 1,3-butylene glycol diacetate, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol Ethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxy-1-butyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether Colored photosensitive resin composition, characterized in that at least one selected from the group consisting of.

[Formula 1]

In Formula 1, A ¹ to A ¹⁶ are each independently Cl, Br or H, 1 to 6 of A ¹ to A ¹⁶ are H, 0 to 5 are Cl, and 5 to 13 are Br. The method according to claim 1,
The compound represented by Formula 1 is a colored photosensitive resin composition, characterized in that contained in an amount of 0.05 to 30% by weight based on the total weight of the colored photosensitive resin composition. The method according to claim 1,
As a weight fraction with respect to the solid content in the colored photosensitive resin composition,
5 to 70% by weight of the colorant (A),
Based on the total weight of the colored photosensitive resin composition,
A colored photosensitive resin composition comprising 60 to 90% by weight of a solvent (E). The method according to claim 1,
A colored photosensitive resin composition, characterized in that the compound represented by Formula 1 and at least one selected from a pigment and a dye are included in a weight ratio of 1: 0.050 to 1: 18.0. The method according to claim 1,
In Formula 1, A ¹ to A ¹⁶ of 1 to 6 are H, 0 to 5 is Cl, and 7 to 13 is a colored photosensitive resin composition, characterized in that Br. The method according to claim 1,
In Chemical Formula 1, 2 to 5 of A ¹ to A ¹⁶ are H, 0 to 3 are Cl, and 8 to 13 are Br. The method according to claim 1,
A colored photosensitive resin composition further comprising at least one additive selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, anti-aggregation agents, and pigment dispersants. The method according to claim 1,
Based on the total weight of the solvent (E),
30 to 95% by weight of a solvent having the boiling point of 100 to 169°C, and
A colored photosensitive resin composition comprising 5 to 70% by weight of a solvent having the boiling point of 170 to 250°C. The method according to claim 1,
A colored photosensitive resin composition, characterized in that the Tmax of the compound represented by Formula 1 is 500 to 530 nm. The method according to claim 1,
T _{50 %} of the compound represented by Formula 1 is 445 to 580 nm, characterized in that the colored photosensitive resin composition. The method according to claim 1,
When y = 0.6 or more in the XYZ color system, x = 0.1 to 0.35 color coordinates, characterized in that the colored photosensitive resin composition. The method according to claim 1,
A colored photosensitive resin composition having a viscosity of 2 to 20 mPa·s on a 25°C basis. A color filter comprising a colored pattern made of the colored photosensitive resin composition according to any one of claims 1 to 12. An image display device comprising the color filter of claim 13.

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