JP2016051176A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition having superior brightness and coloring property and high sensitivity.SOLUTION: The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device. More particularly, the present invention relates to: a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, in which the colorant contains a pigment of a specific structure, and superior brightness and coloring property and high sensitivity are achieved even when the colorant contains a small amount of the pigment; and a color filter and an image display device including the above composition.SELECTED DRAWING: Figure 1

Description

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

  Color filters are widely used in various display devices such as image sensors and liquid crystal display devices (LCDs), and their application range is rapidly expanding. The color filter is composed of three colored patterns of red, green and blue, or three types of yellow, yellow, magenta and cyan. It consists of a colored pattern.

  Each color pattern of the color filter 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. . Color pattern processing using the colored photosensitive resin composition is usually performed in a lithography process.

  On the other hand, various display devices including a solid-state imaging device such as a digital camera have recently been required to have high luminance and high colorability in order to improve processability and quality.

  Korean Patent Application Publication No. 2012-0113666 discloses a resin composition using CI Pigment Green 7 and CI Pigment Yellow 138 and a yellow azo dye. There is a problem of not satisfying at the same time.

Republic of Korea Published Patent No. 2012-0113666

  An object of the present invention is to provide a colored photosensitive resin composition having excellent brightness and colorability and high sensitivity by including a colorant containing a pigment having a specific structure and a photopolymerization initiator containing an oxime compound. And

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

<1> including a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The colorant contains a pigment represented by the following chemical formula 1, and is a colored photosensitive resin composition:

(式中、Ａ^１〜Ａ^１６は、各々独立的に、Ｈ、Ｃｌ、Ｂｒのうちの一つであり、前記Ａ^１〜Ａ^１６のうちのＨは、１〜６個であり、Ｃｌは、０〜５個であり、Ｂｒは、５〜１３個である。)

(Wherein A ^{1 to} A ¹⁶ are each independently one of H, Cl, and Br, and H of A ^{1 to} A ¹⁶ is 1 to 6; Cl is 0 to 5 and Br is 5 to 13)

  <2> The colored photosensitive resin according to <1>, wherein in the pigment of Formula 1, H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13. Composition.

  <3> The colored photosensitive resin according to <1>, wherein in the pigment of the chemical formula 1, H is 2 to 5, Cl is 0 to 3, and Br is 8 to 13. Composition.

  <4> The colored photosensitive resin composition according to <1>, wherein Tmax of the pigment is 500 to 530 nm.

<5> The colored photosensitive resin composition according to <1>, wherein T _50% of the pigment is 450 to 580 nm.

  <6> The colored photosensitive resin composition according to <1>, wherein the colorant is included in an amount of 5 to 70% by weight based on the total solid weight of the photosensitive resin composition.

  <7> The colored photosensitive resin composition according to <1>, wherein in the XYZ color system, when y = 0.6 or more, x = 0.1 to 0.35.

  <8> The colored photosensitive resin composition according to <1>, wherein in the XYZ color system, when y = 0.5 to 0.6, the color coordinate of x = 0.2 to 0.3.

  <9> A color filter formed using the colored photosensitive resin composition according to any one of <1> to <8>.

  <10> An image display device including the color filter according to <9>.

  The colored photosensitive resin composition of the present invention is excellent in luminance and colorability even when a small amount of pigment is contained in the colorant.

  Moreover, the colored photosensitive resin composition of this invention has a high sensitivity by containing a pigment in a small amount.

FIG. 1 is a graph showing a transmission spectrum in the case of using a colorant containing pigments (A-1, A-2), G58 (A-6) and G7 (A-7), each represented by Chemical Formula 1. It is.

  The present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant includes a pigment represented by Chemical Formula 1, so that even if the colorant contains a small amount of pigment, brightness is improved. The present invention relates to a colored photosensitive resin composition having excellent colorability and high sensitivity, a color filter including the same, and an image display device.

  The present invention will be described in detail below.

<Colored photosensitive resin composition>
Colorant The colorant according to the present invention is a component capable of developing a hue such as red / green / blue so as to produce a pattern having a target hue, and is made of ZnPc (Zinc Phthalocyanine) represented by the following chemical formula 1. Including a pigment having a structure.

式中、Ａ^１〜Ａ^１６は、各々独立的に、Ｈ、Ｃｌ、Ｂｒのうち一つであり、Ａ^１〜Ａ^１６のうちＨは、１〜６個であり、Ｃｌは、０〜５個であり、Ｂｒは、５〜１３個である。

In the formula, each of A ^{1 to} A ¹⁶ is independently one of H, Cl, and Br, H of A ^{1 to} A ¹⁶ is 1 to 6, and Cl is 0 to 5 And Br is 5 to 13.

  In the exemplary embodiment of the present invention, the pigment of Formula 1 may have 1 to 6 H, 0 to 5 Cl, and 7 to 13 Br. In another embodiment of the present invention, the pigment of Formula 1 may have 2 to 5 H, 0 to 3 Cl, and 8 to 13 Br. This is preferable because the effect of the present invention is maximized.

  CI Pigment Green 58 (G58) has the advantage of high brightness. However, in order to realize high colorability, the pigment content increases, and if the composition contains a large amount of pigment in this way, there is a risk that the developability will deteriorate and the pattern formed by the composition will be peeled off. There is a problem that sensitivity is lowered.

  However, according to the present invention, by using the pigment represented by the chemical formula 1 as a colorant, high brightness like CI Pigment Green 58 can be exhibited even if the pigment content is small.

  On the other hand, CI Pigment Green 7 (G7) can exhibit high colorability even when the pigment content is low, but has a problem of low luminance. However, the colored photosensitive resin composition of the present invention containing the pigment of the chemical formula 1 shows a transmission spectrum and color coordinates similar to those of CI Pigment Green 7, and has high luminance. Specifically, as can be confirmed from FIG. 1, it has a transmission spectrum at a wavelength of 400 nm to 610 nm similar to that of CI Pigment Green 7.

In this specification, Tmax means the wavelength at the point where the transmittance of the pigment is maximum, and T _50% means the wavelength at the point where the pigment transmittance is 50% or more of the maximum value.

  In one embodiment of the present invention, the Tmax of the pigment is 500 to 530 nm. In this case, the colorability is excellent, which is preferable. More specifically, the Tmax of the pigment may be 495 to 525 nm or 505 to 535 nm.

In another embodiment of the present invention, the T _50% of the pigment is 450 to 580 nm. In this case, the colorability is excellent, which is preferable. More specifically, the T _50% of the pigment may be 445 to 575 nm or 455 to 585 nm.

  If necessary, the colorant according to the present invention may be used as a component capable of developing a hue such as red / green / blue as a component capable of developing a hue having a desired hue, from commonly used pigments and dyes. One or more selected from the group consisting of may be included, and may be manufactured in the form of a mill base.

  In this case, the colorant including the pigment of Formula 1 according to the present invention may have a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system. When y = 0.5-0.6, it can have color coordinates of x = 0.2-0.3.

  The pigment includes an organic pigment and an inorganic pigment. These can be used alone or in admixture of two or more, and it is preferable to use an organic pigment in terms of excellent heat resistance and color developability.

  The organic pigment can be a synthetic dye or a natural dye.

  If necessary, organic pigments can be treated with rosin, surface treatment using pigment derivatives into which acidic groups or basic groups are introduced, graft treatment on the surface of pigments using polymer compounds, etc. In order to remove impurities, the particles may be subjected to cleaning treatment with an organic solvent or water.

  The inorganic pigment can be a metal oxide, a metal complex salt, an inorganic salt of barium sulfate (extreme pigment), or the like.

  Specific examples of the pigment include a compound classified as a pigment by a color index (Color Index, publisher: The Society of Dyer's and Colorists). More specifically, pigments exemplified in the following color index (C.I.) numbers can be included, but the present invention is not limited to this, and it is selected from these according to the desired chromaticity. One or more of these can be co-dispersed using a binder resin, a dispersant, or the like.

  Specific examples of CI pigment yellow include 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. Specific examples of CI pigment orange include 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73. Specific examples of CI pigment red include 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and the like. Specific examples of CI pigment blue include 15: 3, 15: 4, 15: 6, 16, 22, 28, 60, and the like. Specific examples of CI pigment violet include 14, 19, 23, 29, 32, 177 and the like. Specific examples of CI pigment orange include 73. Among the colorants exemplified above, it is preferable to include at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 129, and CI Pigment Yellow 150.

  Specific examples of the dye include C.I. Solvent Yellow 2, C.I. Solvent Yellow 14, C.I. Solvent Yellow 16, C.I. Solvent Yellow 33, C.I. Solvent Yellow 34, C.I. Solvent Yellow 44, CI Solvent Yellow 56, CI Solvent Yellow 82, CI Solvent Yellow 93, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 98, CI Solvent Yellow 98, CI Solvent Yellow 98, CI Solvent Yellow 98, CI Solvent Yellow 98 Solvent Yellow 116, C.I. Solvent Yellow 135; C.I. Solvent Orange 1, C.I. Solvent Orange 3, C.I. Solvent Orange 7, C.I. Solvent Orange 63; C.I. Solvent Red 1, C.I. Solvent Red 2, C.I. Solvent Red 3, C.I. Solvent Red 8, C.I. Solvent Red 18, C.I. Solvent Red 23, C.I. Solvent Red 24, C.I. Solvent Red 27, C.I. Solvent Red 35, C.I. Solvent Red 43, C.I. Solvent Red 45, C.I. Solvent Red 48, CI Solvent Red 49, C.I. Solvent Red 91: 1, C.I. Solvent Red 119, C.I. Solvent Red 135, C.I. Solvent Red 140, C.I. Solvent Red 196, CI Solvent Red 197; CI Solvent Violet 8, C.I. Solvent Violet 9, C.I. Solvent Violet 13, C.I. Solvent Violet 26, C.I. Solvent Violet 28, C.I. CI Solvent Violet 59; C.I. Solvent Blue 4, C.I. Solvent Blue 5, C.I. Solvent Blue 25, C.I. Solvent Blue 35, C.I. Solvent Blue 36, C.I. CI Solvent Blue 38, CI Solvent Blue 70; CI Solvent Green 3, CI Solvent Green 5, CI Solvent Green 7, and the like.

  These pigments and dyes can be used alone or in admixture of two or more.

  The content of the colorant may be included by 5 to 70% by weight, preferably 10 to 50% by weight, based on the solid content in the colored photosensitive resin composition. If the content of the colorant is less than 5% by weight, the color separation ability of the formed pattern can be lowered, and if it exceeds 70% by weight, the lithography performance is lowered and a residue remains or is not developed. Problems can occur.

Binder resin In the present invention, the binder resin is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

  Examples of the monomer having a carboxyl group include methacrylic acid, but are not limited thereto.

  The other monomer capable of copolymerization includes a monomer having a carbon-carbon unsaturated bond. Specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2- Unsaturated carboxylate compounds such as hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl acetate, vinyl propionate, etc. Vinyl carboxylate compounds; vinylcyan compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3 -Unsaturated oxetane carboxylate compounds such as acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane Can do. These monomers can be used alone or in combination of two or more.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0, from the viewpoint of developability. It is.

  The content of the binder resin in the colored photosensitive resin composition is in the range of 5 to 90% by weight, preferably 10 to 70% by weight, based on the total solid content of the colored photosensitive resin composition. If the content of the binder resin is 5 to 90% by weight, the solubility in the developer is sufficient, so that development residues are unlikely to occur on the non-pixel portion of the substrate, and the pixel portion of the exposed portion is reduced during development. Since it is difficult, the non-pixel portion has good dropout characteristics.

Photopolymerizable compound In the present invention, the photopolymerizable compound acts as a monomer that can be polymerized by an active radical, an acid, or the like generated from a photopolymerization initiator described later by light irradiation. The compound is not particularly limited as long as it is a compound that can be polymerized by, but preferably includes a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or a trifunctional or higher polyfunctional photopolymerizable compound. it can.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone, and the like. be able to. Examples of commercially available products include Aronix M-101 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TC-110S (manufactured by Nippon Kayaku Co., Ltd.), and Biscote 158 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). .

  Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di Examples thereof include (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-ethylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (manufactured by Toa Gosei Co., Ltd.), KAYARAD HDDA (manufactured by Nippon Kayaku Co., Ltd.), Biscote 260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), AH -600, AT-600 or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.).

  Specific examples of the 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, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Examples include hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, To-1382 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TMPTA, KAYARAD DPHA, or KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.).

  Moreover, propylene glycol dimethacrylate is also mentioned.

  Among the photopolymerizable compounds exemplified above, tri- or higher functional (meth) acrylates and urethane (meth) acrylates are particularly preferable in that they have excellent polymerizability and can improve strength.

  The said photopolymerizable compound can be used individually or in combination of 2 types or more, respectively.

  The photopolymerizable compound is preferably contained in an amount of 5 to 45% by weight, more preferably 10 to 35% by weight, based on the total solid content in the colored photosensitive resin composition of the present invention. . When the said photopolymerizable compound is contained in the said range, the intensity | strength and smoothness of a pixel part are favorable.

Photopolymerization initiator As long as the photopolymerization initiator can polymerize the binder resin and the photopolymerizable compound, it can be used without any particular limitation on its type, polymerization characteristics, initiation efficiency, From the viewpoint of absorption wavelength and the like, it is preferable to use an oxime compound.

  In one embodiment of the present invention, specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, (Z) -2-((benzoyloxy) imino. ) -1- (4- (phenylthio) phenyl) oxtan-1-one (see Formula 2 below), (E) -1-(((1- (9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl) ethyllysine) amino) oxy) ethaneone (see Formula 3 below) and (E) -1-(((1- (6- (4-((2,2-dimethyl-1,3- Dioxolan-4-yl) methoxy) -2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethyllysine) amino) oxy) ethaneone (see the following chemical formula 4) and the like. It is preferable in terms of excellent brightness and sensitivity.

  The said oxime type compound is not limited to the above-mentioned example, These can be used individually or in mixture of 2 or more types, respectively.

  As commercial products, OXE-01 and OXE-02 manufactured by BASF are typical.

  The content of the oxime compound according to the present invention is not particularly limited as long as its function can be exhibited. For example, the oxime compound can be contained in an amount of 10 to 100% by weight in the total weight of the photopolymerization initiator. When the content of the oxime compound is within the above range, the luminance and sensitivity improvement effect can be maximized.

  In addition to the oxime compound, the colored photosensitive resin composition of the present invention may further contain a photopolymerization initiator that is usually used in the art within a range not damaging the object of the present invention. For example, triazine, acetophenone, biimidazole, benzoin, benzophenone, thioxanthone, and anthracene compounds can be used. These can be used individually or in mixture of 2 or more types.

  The triazine compound is not particularly limited, and examples thereof include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro Methyl) -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-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-Diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( And trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  The acetophenone-based compound is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylcatetal, 2-hydroxy-1- [4. -(2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 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] propan-1-one, 2- And (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  The biimidazole compound is not particularly limited, and examples thereof 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) bi Imidazole, 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 an imidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.

  The benzoin compound is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  The benzophenone-based compound is not particularly limited, and examples thereof include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4 ′. -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like can be mentioned.

  The thioxanthone compound is not particularly limited, and examples thereof include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  The anthracene compound is not particularly limited, and examples thereof include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-. Examples include diethoxyanthracene.

  Other specific examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenyl Examples include methyl glyoxylate and titanocene compounds.

  The content of the photopolymerization initiator is not particularly limited. For example, the content of the photopolymerization initiator is 0.1 to 40% by weight, preferably 1 to 4% based on the total weight of the binder resin and the photopolymerizable compound based on the solid content. It can be included at 30% by weight. If the content of the photopolymerization initiator is within the above range, the effect of improving the brightness and sensitivity can be maximized.

  Moreover, since the colored photosensitive resin composition of the present invention is highly sensitive and the exposure time is shortened, productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion can be improved.

Solvent If the solvent according to the present invention is effective for dissolving other components of the colored photosensitive resin composition of the present invention, the solvent used in the usual colored photosensitive resin composition is specifically limited. Ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like are preferable.

  Specific examples of the solvent 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, and diethylene glycol dipropyl. Diethylene glycol dialkyl ethers such as ether and diethylene glycol dibutyl ether; alkylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monop Alkylene glycol alkyl ether acetates such as propyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerine; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolollactone And amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

  An example thereof is ethyl 3-ethoxypropanoate.

  Of the solvents exemplified above, in view of coating properties and drying properties, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferable, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate and Mention may be made of esters such as methyl 3-methoxypropionate. More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be mentioned. These solvents can be used alone or in admixture of two or more.

  The content of the solvent in the colored photosensitive resin composition of the present invention may be included by 60 to 90% by weight, preferably 70 to 90% by weight with respect to the total weight of the colored photosensitive resin composition. It may be contained at 85% by weight. When the solvent is in the range of 60 to 90% by weight, it provides an effect that the coating property is good when applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also called a die coater), and an ink jet. To do.

Additives The colored photosensitive resin composition of the present invention is optionally added with other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, anti-aggregation agents, pigment dispersants, and the like. Can further be included.

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

  The curable resin is used in order to increase deep curing and mechanical strength. Specific examples of the curable resin include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

  In the curing agent, specific examples of the epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, and the like. Aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of the above epoxy resins, epoxy resins, and aliphatic, alicyclic or aromatic other than brominated derivatives thereof An epoxy group compound, a butadiene (co) polymer epoxidized product, an isoprene (co) polymer epoxidized product, a glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate and the like. Specific examples of the oxetane compound include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  The curable resin may be used in combination with a curable resin and a curing auxiliary compound that enables ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. What is marketed as an epoxy resin hardening | curing agent can be used for the said polyhydric carboxylic acid anhydrides. Specific examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), and MH-700 (manufactured by Shin Nippon Rika Co., Ltd.). ) And the like. The exemplified curing agents can be used alone or in admixture of two or more.

  The surfactant can be used to further improve the formation of the colored photosensitive resin composition film, and a fluorine-based surfactant or a silicon-based surfactant can be used.

  Examples of the silicon-based surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400 manufactured by Dow Corning Toray Silicon Co., Ltd., TSF-4440, TSF-4300, TSF-4445, GE Toshiba Silicon Co., Ltd. There are TSF-4446, TSF-4460, TSF-4442, and the like. Examples of the fluorosurfactant include Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink and Chemicals, Inc. as commercially available products. The exemplified surfactants can be used alone or in admixture of two or more.

  The adhesion promoter is preferably a silane compound. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-amino. Propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Isocyanate B pills trimethoxysilane, and 3-isocyanate propyl triethoxysilane and the like. The exemplified adhesion promoters can be used alone or in admixture of two or more.

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

  Specific examples of the antioxidant include 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-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 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-methyl Nor), 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, pentaerythritol tetrakis (3- Lauryl thiopropionate), 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- ert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di -T-butyl-4-methylphenol and the like can be mentioned.

  Specific examples of the aggregation inhibitor include sodium polyacrylate.

  As the pigment dispersant, those commonly used in the art can be used without limitation as added for deaggregating the pigment and maintaining safety. Preferably, an acrylate dispersant (hereinafter also referred to as “acrylic dispersant”) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) can be used. Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, DISPER BYK LPN-6919, and the like. The acrylic dispersants exemplified above can be used alone or in combination of two or more.

  As the pigment dispersant, other resin type pigment dispersants may be used in addition to the above-described acrylic dispersant.

  Examples of the other resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partially) amine salts of polycarboxylic acids, and polycarboxylic acids. Ammonium salts, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or polyesters and poly (lower alkylene imines having glass carboxyl groups) ) Or amides formed by the reaction of ()) or oily dispersants such as salts thereof; (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl Alcohol or polyvinyl Water-soluble resins or water-soluble polymer compounds such as loridone; polyesters; modified polyacrylates; addition products of ethylene oxide / propylene oxide and phosphate esters.

  Commercial products of the resin type pigment dispersant include cationic resin dispersants. For example, BYK Chemie's trade names: 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: 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 name of Lubilzol: SOLPERS-240 0, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; trade names of Ajinomoto Co., Inc .: AJISPER PB- 821, Azisper PB-822, Azisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA-33, FLOREN DOPA-44, and the like.

<Color filter>
Moreover, this invention provides the color filter manufactured with the said colored photosensitive resin composition.

  The color filter of the present invention includes a substrate and a colored pattern produced from the colored photosensitive resin composition on the substrate.

  The substrate is made of a transparent material having sufficient strength and support for the safety of the color filter. Preferably, a glass having excellent chemical safety and high strength can be used.

  The colored pattern is produced by applying the colored photosensitive resin composition on a substrate, photocuring and developing.

  The thickness of a coloring pattern is not specifically limited, For example, it is 1-6 micrometers.

  The colored pattern can be formed by the following method, for example.

  First, the composition is applied onto a substrate or a layer made of a solid content of a previously formed photosensitive resin composition, and pre-baked from the applied photosensitive resin composition layer to remove volatile components such as a solvent. Thus, a smooth coating film is obtained.

  The coated film thus obtained is irradiated with ultraviolet rays through a mask in order to form a target pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned.

  Thereafter, the cured pattern is brought into contact with an aqueous alkaline solution to dissolve the non-exposed portion and developed, whereby the intended pattern development can be obtained.

  The developing method may be any of a liquid addition method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.

  As the coating method, for example, spin coating, flexible coating method, roll coating method, slit and spin coating, or slit coating method is performed.

  After the application, the colored photosensitive resin composition layer is formed by volatilizing volatile components such as a solvent by heating after drying (pre-baking) or drying under reduced pressure. Here, heating temperature is 70-200 degreeC normally, Preferably, it is 80-130 degreeC.

  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 either an inorganic or organic alkaline compound.

  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, silicic acid. Examples thereof include sodium, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, Examples include ethanolamine. 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 alkaline developer is, for example, 0.01 to 10% by weight, and 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, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned.

  Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzenesulfonate And alkylaryl sulfonates such as sodium dodecylnaphthalene sulfonate; and the like.

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

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

  The concentration of the surfactant in the alkali 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 development, it is washed with water, and if necessary, post-baking may be carried out at 150 to 230 ° C. for 10 to 60 minutes.

<Image display device>
The present invention also provides an image display device including the color filter.

  Specifically, as the image display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a mobile terminal such as a mobile phone Display devices such as display devices for digital cameras, display devices for digital cameras, display devices for car navigation, and particularly color display devices are suitable.

  Hereinafter, preferred examples will be presented to help understanding of the present invention. However, this is only a preferred embodiment of the present invention, and does not limit the scope of the present invention. Any equivalent changes and additions made based on the specification and drawings of the present invention are not limited to this embodiment. It is intended to be included within the scope of the claims.

Examples and Comparative Examples Colored photosensitive resin compositions having the compositions and contents (parts by weight) described in Table 1 below were produced. The colorants A-1 to A-5 are pigments having a structure represented by the chemical formula I.

Ａ−１：ＤＩＣ社、Ｃｌ：２個、Ｂｒ：９個、Ｈ：５個(Ｔｍａｘ：５１５、Ｔ_５０％：４５０〜５７５nm)
Ａ−２：ＤＩＣ社、Ｃｌ：１個、Ｂｒ：１０個、Ｈ：５個(Ｔｍａｘ：５１５、Ｔ_５０％：４５０〜５７５nm)
Ａ−３：ＤＩＣ社、Ｃｌ：１個、Ｂｒ：１１個、Ｈ：４個(Ｔｍａｘ：５２０、Ｔ_５０％：４５５〜５８０nm)
Ａ−４：ＤＩＣ社、Ｃｌ：１個、Ｂｒ：１２個、Ｈ：３個(Ｔｍａｘ：５２０、Ｔ_５０％：４５５〜５８０nm)
Ａ−５：ＤＩＣ社、Ｃｌ：３個、Ｂｒ：８個、Ｈ：５個(Ｔｍａｘ：５１０、Ｔ_５０％：４４５〜５７０nm)
Ａ−６：Ｇ５８(化学式１の構造中、中心原子がＺｎであり、Ａ^１〜Ａ^１６は、Ｈ：０〜１個、Ｃｌ：０〜１個、Ｂｒ：１４〜１６個の混合物)
Ａ−７：Ｇ７(化学式１の構造中、中心原子がＣｕであり、Ａ^１〜Ａ^１６は、Ｈ：０〜２個、Ｃｌ：１４〜１６個の混合物)
Ａ−８：Ｙ１２９(製造社：ＤＩＣ社)
Ｂ：メタクリル酸：ベンジルメタクリレート＝３１：６９(モル比)、重量平均分子量＝３０,０００、酸価＝１０５のメタクリル酸とベンジルメタクリレートの共重合体
Ｃ：ジペンタエリトストールヘキサアクリレート(ＫＡＹＡＲＡＤ ＤＰＨＡ；製造社：日本化薬(株))
Ｄ−１：ＯＸＥ−０１(製造社：Ｃｉｂａ社)
Ｄ−２：ＯＸＥ−０２(製造社：Ｃｉｂａ社)
Ｄ−３：２−メチル−１−(４−メチルチオフェニル)−２−モルホリノプロパン−１−オン
Ｅ−１：プロピレングリコールモノメチルエーテルアセテート
Ｅ−２：エチル３−エトキシプロピオネート
Ｆ−１：シリコン系界面活性剤(ＳＨ−８４００)
Ｆ−２：アクリル系顔料分散剤(ＤＩＳＰＥＲ ＢＹＫ−２００１、製造社: ビックケミー(ＢＹＫ))
Ｆ−３：密着促進剤(３−メタクリルオキシプロピルトリメトキシシラン)

A-1: DIC, Cl: 2, Br: 9, H: 5 (Tmax: 515, T _50% : 450-575 nm)
A-2: DIC Corporation, Cl: 1, Br: 10, H: 5 (Tmax: 515, T _50% : 450-575 nm)
A-3: DIC Corporation, Cl: 1, Br: 11, H: 4 (Tmax: 520, T _50% : 455-580 nm)
A-4: DIC Corporation, Cl: 1, Br: 12, H: 3 (Tmax: 520, T _50% : 455-580 nm)
A-5: DIC, Cl: 3, Br: 8, H: 5 (Tmax: 510, T _50% : 445 to 570 nm)
A-6: G58 (in the structure of Chemical Formula 1, the central atom is Zn, and A ^{1 to} A ¹⁶ are a mixture of H: 0 to 1, Cl: 0 to 1, Br: 14 to 16)
A-7: G7 (in the structure of Chemical Formula 1, the central atom is Cu, A ^{1 to} A ¹⁶ are a mixture of H: 0 to 2, Cl: 14 to 16)
A-8: Y129 (manufacturer: DIC)
B: Copolymer of methacrylic acid and benzyl methacrylate having methacrylic acid: benzyl methacrylate = 31: 69 (molar ratio), weight average molecular weight = 30,000, and acid value = 105 C: dipentaerythritol hexaacrylate (KAYARAD DPHA; (Manufacturer: Nippon Kayaku Co., Ltd.)
D-1: OXE-01 (manufacturer: Ciba)
D-2: OXE-02 (manufacturer: Ciba)
D-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one E-1: Propylene glycol monomethyl ether acetate E-2: Ethyl 3-ethoxypropionate F-1: Silicon -Based surfactant (SH-8400)
F-2: Acrylic pigment dispersant (DISPER BYK-2001, manufacturer: Big Chemie (BYK))
F-3: Adhesion promoter (3-methacryloxypropyltrimethoxysilane)

Production Example: Production of Color Filter A color filter was produced using the colored photosensitive resin composition produced in Examples 1 to 9 and Comparative Examples 1 to 5.

Each colored photosensitive resin composition was applied onto a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Thereafter, a pattern for changing the transmittance stepwise in the range of 1 to 100% and a test photomask having a line / space pattern of 1 μm to 50 μm are placed on the thin film, and the distance from the test photomask is set. Was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with an illuminance of 100 mJ / cm ² using a 1 KW high-pressure mercury lamp containing all of g, h, and i rays, and no special optical filter was used. The thin film irradiated with the ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass plate on which the thin film was formed was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 1 hour to produce a color filter. The film thickness of the manufactured color filter was 2.0 μm.

Experimental Example 1: Luminance measurement The luminance was measured using a microspectroscope OSP-SP2000. The results are shown in Table 2 below.

Experimental Example 2: Measurement of chromaticity (color coordinates) The color coordinates of the colored layer were measured using a microspectroscope OSP-SP2000. The results are shown in Table 2 below.

Experimental Example 3: Proceeding in the same way as the luminance measurement method except that a pattern mask that changes the sensitivity measurement transmittance in a stepwise manner in the range of 1 to 100% was used, (film thickness before development / after development) Film thickness) X 100) The minimum exposure amount at which ≧ 90% was displayed as sensitivity. The results based on the following evaluation criteria are shown in Table 3.

◎ Evaluation criteria When the pattern remains with a sensitivity of less than 60 (mJ / cm ² ): ○
When the pattern remains with a sensitivity of 60 (mJ / cm ² ) or more: X

  Referring to Tables 2 and 3, it was found that the examples belonging to the scope of the present invention had higher luminance than the comparative examples. Of the comparative examples, it was found that when the luminance value is similar to that of the example, the sensitivity is somewhat lower than that of the example.

Claims (10)

Including a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent;
The colored photosensitive resin composition, wherein the colorant contains a pigment represented by the following chemical formula 1.
[Chemical 1]

(Wherein A ^{1 to} A ¹⁶ are each independently one of H, Cl, and Br, and H of A ^{1 to} A ¹⁶ is 1 to 6; Cl is 0 to 5 and Br is 5 to 13)   2. The colored photosensitive composition according to claim 1, wherein in the pigment of Formula 1, H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13. 3. Resin composition.   2. The colored photosensitive composition according to claim 1, wherein in the pigment of Formula 1, H is 2 to 5, Cl is 0 to 3, and Br is 8 to 13. 3. Resin composition.   The colored photosensitive resin composition according to claim 1, wherein Tmax of the pigment is 500 to 530 nm. 5. The colored photosensitive resin composition according to claim 1, wherein T _50% of the pigment is 450 to 580 nm.   The colored photosensitive resin composition according to claim 1, wherein the colorant is included in an amount of 5 to 70% by weight based on the total solid content of the photosensitive resin composition. .   7. The colored photosensitive resin according to claim 1, wherein in the XYZ color system, when y = 0.6 or more, the color photosensitive resin has a color coordinate of x = 0.1 to 0.35. Composition.   7. The coloring according to claim 1, wherein in the XYZ color system, when y = 0.5 to 0.6, the color coordinates are x = 0.2 to 0.3. Photosensitive resin composition.   It forms using the colored photosensitive resin composition of any one of Claims 1-8, The color filter characterized by the above-mentioned.   An image display device comprising the color filter according to claim 9.

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