JP2017102431A - Colored photosensitive resin composition, and color filter and image display device manufactured by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition excellent in application property, development speed, adhesiveness and sensitivity.SOLUTION: The colored photosensitive resin composition comprises an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, in which the alkali-soluble resin contains a tricyclodecanyl (meth)acrylate structural unit and an alkyl (meth)acrylate structural unit, and the photopolymerization initiator contains a compound represented by chemical formula below. A color filter and an image display device manufactured by using the above composition are also disclosed.SELECTED DRAWING: None

Description

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

  The color filter is widely used in various display devices such as an image sensor and a liquid crystal display device (LCD), and its application range is rapidly expanded. The color filter is composed of three colored patterns of red, green, and blue, or three colored patterns of yellow, yellow, magenta, and cyan. Become.

  Each colored 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 by a lithography process.

  As such a colored photosensitive resin composition, a composition containing a photopolymerizable compound and a photopolymerization initiator together with a pigment and a binder resin is often used.

  The current display is rapidly increasing in high-resolution models for more practical image transmission, especially for panels applied to mobile and tablet PCs, which are personal portable devices, with higher precision of 500 ppi or higher. There is a demand for a pixel size smaller than that of a TV or monitor that is viewed from a relatively long distance.

  As the precision becomes higher, the area of the black matrix must be larger in order to put more pixels in a limited space. However, if this happens, the aperture ratio will be low and sufficient brightness will not be obtained, and many black matrix patterns may cause problems in flatness when applying resist, and there may be uncoated areas. is there.

  Such a problem has recently been recognized as a problem that occurs on the way to high precision display, and in order to solve the above-mentioned problem, the content of resist solids is not only reduced to lower the viscosity. There was no special solution.

  However, when the viscosity is lowered by simply reducing the solid content, the flatness at the time of application by the slit coater is greatly affected, and there is a disadvantage in that unevenness of brightness occurs and defects increase. For example, Patent Document 1 discloses the contents relating to the colored photosensitive resin composition, but the conventional technology has a problem that the flatness is inferior because the coating performance is poor and the developing speed is also inferior.

Korean Published Patent No. 10-2009-098077

  An object of this invention is to provide the colored photosensitive resin composition excellent in applicability | paintability, image development speed, adhesiveness, and a sensitivity.

  Moreover, an object of this invention is to provide the color filter and image display apparatus which were manufactured using the said colored photosensitive resin composition and were excellent in the brightness | luminance.

  In order to achieve the above object, the colored photosensitive resin composition of the present invention comprises an alkali-soluble resin; a photopolymerizable compound and a photopolymerization initiator, wherein the alkali-soluble resin is a structural unit represented by the following chemical formula 1 And the structural unit represented by Chemical Formula 2, wherein the photopolymerization initiator includes a compound represented by Chemical Formula 3 below.

[Chemical Formula 1]

[Chemical formula 2]

[Chemical formula 3]

  In Formula 1, R1 is hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms with or without heteroatoms, or an aromatic hydrocarbon having 6 to 12 carbon atoms with or without heteroatoms, n Is an integer of 1 to 500, and in Formula 2, R2 is hydrogen or an alkyl group having 1 to 12 carbon atoms, R3 is a linear alkyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. A branched alkyl group, m is an integer of 1 to 500, and in Formula 3, R4 to R7 are independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or 3 to 20 carbon atoms Cyclo R8 to R14 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl having 7 to 40 carbon atoms. An alkyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group, or a hydroxy group, and p is , 0 or 1.

  Moreover, this invention provides the color filter manufactured with the said colored photosensitive resin composition, and an image display apparatus containing the same.

  The colored photosensitive resin composition of the present invention can provide a colored photosensitive resin composition having excellent coatability, development speed, adhesion and sensitivity.

  Moreover, the color filter and image display apparatus manufactured using the colored photosensitive resin composition of the present invention have excellent luminance characteristics.

1 is a view of sensitivity evaluation using a colored photosensitive resin composition manufactured according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in more detail.

  When a member according to the present invention is positioned “on” another member, this is not only when the member is in contact with the other member, but also when there is another member between both members. Including.

  When a component that is a part of the present invention is “including” a component, this means that the component can further include other components than the other components, unless specifically stated to the contrary. .

  The present invention provides a colored photosensitive resin composition and a color filter using the same.

Alkali-soluble resin The alkali-soluble resin of the present invention comprises a structural unit represented by the following chemical formula 1 and a structural unit represented by the following chemical formula 2.

[Chemical Formula 1]

[Chemical formula 2]

  In Formula 1, R1 is hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms with or without heteroatoms, or an aromatic hydrocarbon having 6 to 12 carbon atoms with or without heteroatoms, n Is an integer of 1 to 500, and in Formula 2, R2 is hydrogen or an alkyl group having 1 to 12 carbon atoms, and R3 is a linear alkyl group having 2 to 20 carbon atoms, or 2 to 2 carbon atoms. 20 branched alkyl groups, and m is an integer from 1 to 500.

  Specifically, in Formula 2, R2 is hydrogen or a methyl group.

  The alkali-soluble resin containing the structural units of Chemical Formula 1 and Chemical Formula 2 is not limited to a form. That is, the structural unit may be in the form of a block copolymer in which the structural units are repeated constantly, or in the form of a random copolymer in which the structural units are repeated at random.

  Specific examples of the monomer related to the structural unit of Formula 1 include, for example, epoxidized dicyclodecanyl (meth) acrylate-3,4-epoxytricyclodecan-8-yl (meth) acrylate, 3,4-epoxy. Tricyclodecan-8-yl (meth) acrylate, epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecan-9-yloxy) ethyl (meth) acrylate, 2- ( 3,4-epoxytricyclodecan-8-yloxy) ethyl (meth) acrylate, epoxidized dicyclopentanyloxyhexyl (meth) acrylate, and the like. Among these, particularly preferable examples include epoxidized dicyclodecanyl (meth) acrylate and epoxidized dicyclopentanyloxyethyl (meth) acrylate. Here, (meth) acrylate means acrylate and / or methacrylate.

Specific examples of the monomer related to the structural unit of Formula 2 include ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, and n-butyl. Acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, 2-methyl Butyl acrylate, 2-methylbutyl methacrylate, 2-ethylpropyl acrylate, 2-methylbutyl methacrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethyl Xyl acrylate, 2-ethylhexyl methacrylate, n-heptyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate, stearyl acrylate, stearyl methacrylate, 2, 2,3,3-tetrafluoropropyl acrylate, 3-trimethoxysilylpropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3 -Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydro Sibutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, Methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl alcohol Unsaturated carboxylic acid esters such as acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; and polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane polymers Examples thereof include giant monomers having a monoacryloyl group or a monomethacryloyl group at the terminal.

  In addition, the alkali-soluble resin may further include a structural unit represented by the following chemical formula 4.

[Chemical formula 4]

  In Formula 4, R15 and R17 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, R16 is a residue containing a carboxylic acid derived from an acid anhydride, and q is 1 It is an integer of ~ 500.

  Examples of the acid anhydride include phthalic anhydride, (2-dodecen-1-yl) succinic anhydride ((2-Dodecen-1-yl) succinic anhydride), and maleic anhydride. , Succinic anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride, 3-dimethyl anhydride -Dimethylglutanic anhydride), phenylsuccinic anhydride, octopus Acid anhydride (Itaconic anhydride), 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalic anhydride), trimethyl anhydride (Trimellitic anhydride), hexahydrophthalic anhydride ( 1 or more types selected from the group which consists of Hexahydrophthalic anhydride and Carbic anhydride (Carbic anhydride) are included.

  In the present invention, when the alkali-soluble resin additionally contains the structural unit of Chemical Formula 4, since it can have a glass transition temperature of less than 0 ° C., the transparency is excellent and the luminance is increased. In this case, it is possible to manufacture a color filter having excellent quality by improving the coating ability at the time and suppressing uneven brightness and uncoating phenomenon.

  The alkali-soluble resin may include 1 to 99 mol% of the structural unit represented by the chemical formula 1 with respect to the total content of the constituent units constituting the alkali-soluble resin. In addition, the structural unit represented by Chemical Formula 2 may be included at 1 to 99 mol% with respect to the total content of the structural units constituting the alkali-soluble resin. The structural unit represented by Chemical Formula 4 may be included at 1 to 99 mol% with respect to the total content of the structural units constituting the alkali-soluble resin.

  When the structural unit represented by the chemical formula 1, the structural unit represented by the chemical formula 2, or the structural unit represented by the chemical formula 4 is included in the mol% range, the developability, the solubility, and the balance with the dye Has an advantage that a good alkali-soluble resin can be obtained.

  In addition, the alkali-soluble resin may be produced by copolymerization using an additional monomer containing an unsaturated double bond.

The kind of the monomer containing the unsaturated double bond is not particularly limited, and specifically, for example, styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxy. Such as styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether Aromatic vinyl compounds;
N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm -N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1. ^O2,6 ] decan-8-yl (meth) acrylate, alicyclic (meth) acrylates such as 2-dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; and 3- (methacryloyloxy Methyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxy) Unsaturated oxetanes such as methyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane.

  The said monomer containing an unsaturated double bond can be used individually or in mixture of 2 or more types, respectively.

  Although the content of the monomer containing the unsaturated double bond is not particularly limited, the alkali-soluble resin is preferably contained at 5 to 50 mol% with respect to the total content of the constituent units constituting the alkali-soluble resin.

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

  When the acid value of the alkali-soluble resin is within the above range, the colored photosensitive resin composition can ensure a sufficient development speed, and the adhesion between the substrate and the colored photosensitive resin composition is reduced, resulting in a pattern. The phenomenon that the short circuit occurs can be prevented, and since the compatibility with the dye is excellent, the phenomenon that the dye is deposited can be prevented. Moreover, there exists an advantage which can prevent generation | occurrence | production of the problem which the viscosity rises by preventing the phenomenon that the storage stability of a coloring photosensitive resin composition falls.

  In the present invention, the alkali-soluble resin is preferably contained at 10 to 80% by weight, more preferably 10 to 70% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. Within the range of 10 to 80% by weight, the solubility in the developer is sufficient, pattern formation is facilitated, and the film reduction of the pixel portion of the exposed portion during development can be prevented, and the leakage of the non-pixel portion can be improved. .

Photopolymerizable compound In the present invention, the photopolymerizable compound is a compound that can be polymerized by the action of a photopolymerization initiator described later, and a monofunctional monomer, a bifunctional monomer, or a polyfunctional monomer can be used. Specifically, a bifunctional or higher polyfunctional monomer can be used.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl pyrrolidone. Although it is mentioned, it is not limited to this.

  Examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Bis (acryloyloxyethyl) ether or 3-methylpentanediol di (meth) acrylate or the like, but is not limited thereto.

  Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, propoxylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylatet dipentaerythritol hexa (meth) acrylate, propoxylatet dipentaerythritol hexa (meth) acrylate or dipentaerythritol hexa ( Examples include, but are not limited to, (meth) acrylate.

  The photopolymerizable compound is preferably contained at 5 to 45% by weight, more preferably 7 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 45% by weight.

Photopolymerization initiator The oxime ester fluorene initiator, which is a feature of the present invention, together with the acrylic binder resin is used for improving the sensitivity of the colored photosensitive resin composition. The photopolymerization initiator is a compound for initiating the photopolymerizable compound. In the present invention, the oxime ester fluorene initiator represented by the following chemical formula 3 is used to increase the color photosensitive resin composition. Sensitivity is increased to shorten the exposure time, thereby improving patternability and providing high resolution.

[Chemical formula 3]

In Formula 3, R4 to R7 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 7 to 40 carbon atoms. An arylalkyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and R8 to R14 are each independently hydrogen, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and 2 carbon atoms A hydroxyalkoxyalkyl group having ˜40, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group, and p is 0 or 1 A.
The halogen referred to in the present invention is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

  The alkyl group referred to in the present invention means a straight-chain or side-chain hydrocarbon radical consisting only of carbon and hydrogen atoms, having no unsaturation, and bonded to the rest of the molecule by a single bond. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms. A branched alkyl group is most preferred. Examples of such unsubstituted alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isoamyl. Group, hexyl group and the like. One or more hydrogen atoms contained in the alkyl group are a halogen atom, a hydroxy group, a thiol group (—SH), a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone group, a carboxyl group, a sulfone group. Acid group, phosphoric acid group, alkyl group having 1 to 20 carbon atoms, halogenated alkyl group having 1 to 20 carbon atoms, alkenyl group having 1 to 20 carbon atoms, alkynyl group having 1 to 20 carbon atoms, 1 to carbon atoms Substitution with a 20 heteroalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, or a heteroarylalkyl group having 6 to 20 carbon atoms Can do.

  The alkoxy group referred to in the present invention is preferably an oxygen-containing linear or branched alkoxy group each having an alkyl moiety having 1 to 20 carbon atoms. An alkoxy group having 1 to 10 carbon atoms is more preferable, and an alkoxy group having 1 to 4 carbon atoms is most preferable. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and t-butoxy groups. The alkoxy group can be further substituted with one or more halo atoms such as fluoro, chloro or bromo to provide a haloalkoxy group. Examples thereof include a fluoromethoxy group, a chloromethoxy group, a trifluoromethoxy group, a trifluoroethoxy group, a fluoroethoxy group, and a fluoropropoxy group. One or more hydrogen atoms in the alkoxy group can be substituted with the same substituent as in the alkyl group.

  The cycloalkyl group referred to in the present invention includes not only a monocyclic system but also a polycyclic hydrocarbon, and at least one hydrogen atom in the cycloalkyl group is a substituent similar to the case of the alkyl group. It can be replaced. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and most preferably a cycloalkyl group having 3 to 8 carbon atoms.

  The aryl group referred to in the present invention means an aromatic monocyclic or multicyclic hydrocarbon ring system consisting only of hydrogen and carbon, where the ring system can be partially or fully saturated. At least one or more hydrogen atoms in the aryl group can be substituted with the same substituent as in the alkyl group. The aryl group is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen and is a single or fused, suitably containing 4 to 7, preferably 5 or 6 ring atoms in each ring Including a ring system, including a form in which a plurality of aryls are linked by a single bond. The aryl group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 18 carbon atoms.

  The hydroxyalkyl group referred to in the present invention means an OH-alkyl group in which a hydroxy group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group has the hydroxyalkyl group and the alkyl group linked to oxygen. Mean hydroxyalkyl-O-alkyl. The hydroxyalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 2 to 9 carbon atoms.

  The arylalkyl group referred to in the present invention means that one or more hydrogen atoms of the alkyl group are substituted with the aryl group. The arylalkyl group preferably has 7 to 40 carbon atoms, more preferably 7 to 28 carbon atoms, and most preferably 7 to 24 carbon atoms.

  The oxime ester fluorene-based initiator represented by the chemical formula 3 may be represented by the following chemical formula 5 when p is 0 or 1, and when p is 0, It can be represented by the following chemical formula 6.

[Chemical formula 5]

  In Formula 5, R18 to R21 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 7 to 7 carbon atoms. A arylalkyl group having 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms; A is hydrogen, 1 to 20 carbon atoms An alkyl group, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, and a hydroxyalkoxyalkyl having 2 to 40 carbon atoms A cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group.

  Specifically, R18 to R21 are hydrogen, bromine, chlorine, iodine, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n- Propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n-propyl group, hydroxy n-butyl group, hydroxy i-butyl group Hydroxy n-pentyl group, hydroxy i-pentyl group, hydroxy n-hexyl group, hydroxy i-hexyl group, hydroxymeth A dimethyl group, a hydroxymethoxyethyl group, a hydroxymethoxypropyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a hydroxyethoxyhexyl group; A is hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, phenyl group, naphthyl group, biphenyl group, terphenylanthryl group , Indenyl group, phenanthryl group, methoxy group, ethoxy group, propyloxy group, butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxymethoxymethyl group, hydroxymethoxy group It can be an ethyl group, a hydroxymethoxypropyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, an amino group, a nitro group, a cyano group or a hydroxy group. It is not limited.

  Preferably, R18 and R19 are each independently hydrogen or an n-butyl group; R20 is a methyl group; R21 is a methyl group, an n-butyl group or a phenyl group; A is hydrogen or It can be a nitro group. R18 and R19 are preferably the same.

  Typical examples of the oxime ester fluorene-based initiator represented by the chemical formula 5 include the following compounds, but the oxime ester fluorene-based initiators are not limited to the following examples. Is possible.

[Chemical formula 6]

  In Formula 6, R22 to R32 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 7 to 7 carbon atoms. A 40-arylalkyl group, a C1-C20 hydroxyalkyl group, a C2-C40 hydroxyalkoxyalkyl group, or a C3-C20 cycloalkyl group.

  Specifically, R22 to R32 are hydrogen, bromine, chlorine, iodine, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n- Propyloxy group, i-propyloxy group, n-butoxy group, i-butoxy group, t-butoxy group, hydroxymethyl group, hydroxyethyl group, hydroxy n-propyl group, hydroxy n-butyl group, hydroxy i-butyl group Hydroxy n-pentyl group, hydroxy i-pentyl group, hydroxy n-hexyl group, hydroxy i-hexyl group, hydroxymeth Can be a dimethyl group, a hydroxymethoxyethyl group, a hydroxymethoxypropyl group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a hydroxyethoxyhexyl group .

  Preferably, R22 and R23 are each independently hydrogen, a methyl group, an ethyl group, a propyl group, or a butyl group; R24 is a methyl group, an ethyl group, or a propyl group; R25 is a methyl group , An ethyl group, a propyl group, or a butyl group; R26 to R32 may be hydrogen. R22 and R23 are preferably the same.

  Typical examples of the oxime ester fluorene-based initiator represented by the chemical formula 6 include the following compounds. However, the oxime ester fluorene-based initiator is not limited to the following examples and is suitable for the above-described conditions, and is known in this field. Everything is usable.

  The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the whole colored photosensitive resin composition, Preferably it may be contained at 0.1 to 1% by weight. When the content of the photopolymerization initiator is within the above range, it is possible to prevent a phenomenon in which sensitivity is lowered and pattern loss occurs during the development process, and excessive crosslinking reaction occurs due to excessive reaction. Thus, it is possible to prevent the phenomenon that the physical properties of the coating film that causes wrinkles are deteriorated.

  Photopolymerization initiators other than those described above can be additionally used as long as the effects of the present invention are not damaged. As the photopolymerization initiator that can be additionally used, for example, one or more compounds selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, non-imidazole compounds, and thioxanthone compounds may be used. preferable.

  Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 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- (4-methylbenzyl) -2- And (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

  Examples of the benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4 ″ -tetra (tert-butylperoxy). And carbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

  Examples of the triazine compound include 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-methoxy Styryl) -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 And ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. .

  Examples of the non-imidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl nonimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenyl non-imidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) non-imidazole, 2,2′-bis (2-Chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) nonimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl Examples thereof include -1,2′-non-imidazole and imidazole compounds in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted with a carboalkoxy group. Among the non-imidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl non-imidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl non-imidazole and 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-nonimidazole are preferably used. .

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  The photopolymerization initiator may further contain a photopolymerization initiation auxiliary agent 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 can further improve sensitivity and increase productivity by including a photopolymerization initiation auxiliary agent.

  As the photopolymerization initiation auxiliary agent, for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfide having a thiol group can be preferably used.

  Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone) and 4,4′-bis (diethylamino) An aromatic amine compound such as benzophenone can be used, and an aromatic amine compound is preferably used as the amine compound.

  Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, Mention may be made of aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, nabutylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  Examples of the organic sulfide 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, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis ( 3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

  Such a photopolymerization initiation auxiliary agent is preferably used in an amount of 10 mol or less, more preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is used within the above range, it is possible to increase the polymerization efficiency and expect an improvement in productivity.

The solvent solvent is used for dissolving other components of the colored photosensitive resin composition of the present invention, and is used without particular limitation as long as it is a solvent used for a commonly used colored photosensitive resin composition. 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, ethylene glycol monobutyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Methyl cellosolve acetate Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; benzene , Toluene, xylene, mesitylene and other aromatic hydrocarbons; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and other alcohols Class: Ethyl 3-ethoxypropionate Esters such as 3-methyl propionate, and cyclic esters such as γ- butyrolactone.

  The solvent is preferably an organic solvent having a boiling point of 100 to 200 ° C. in terms of coating properties and drying properties. For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3- Examples thereof include ethyl ethoxypropionate and methyl 3-propionate. The solvents exemplified above can be used alone or in admixture of two or more.

  The above exemplified solvents may be used alone or in combination of two or more. Moreover, 60 to 90 weight% is preferable with respect to the colored photosensitive resin composition total weight of this invention, More preferably, the said solvent is contained by 70 to 85 weight%. If the solvent is contained in the range of 60 to 90% by weight, a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), a spray coater, reverse printing, gravure printing, screen printing, Applicability when coated by a coating apparatus such as pad printing or inkjet is improved.

Colorant In the present invention, the colorant may comprise one or more pigments, one or more dyes, or a mixture thereof.

  As the pigment, an organic pigment or an inorganic pigment generally used in the art can be used. The pigment may be finely divided by resin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, if necessary, graft treatment of the pigment surface with a polymer compound, sulfuric acid atomization method, etc. It is also possible to carry out a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment of ionic impurities by an ion exchange method, or the like.

  As the organic pigment, various pigments used in printing inks, inkjet inks and the like can be used. Specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments. Perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavantron pigments, pyranthrone pigments, diketopyrrolopyrrole pigments.

  Further, as the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples include metal oxides or composite metal oxides such as antimony, carbon black, organic black pigments, titanium black and pigments which are mixed with red, green and blue.

  In particular, examples of the organic pigment and the inorganic pigment include compounds classified as pigments by a color index (published by The Society of Dyers and Colorists), and more specifically, as follows. Examples of pigments having various color index (CI) numbers can be mentioned, but the pigments are not necessarily limited thereto.

C. I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;
C. I. Pigment green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;
C. I pigment brown 28;
C. Mention may be made of pigments such as I pigment black 1 and 7.

  The pigments can be used alone or in admixture of two or more.

  Also preferably, C.I. Pigment Orange 38; C.I. CI pigment red 166, 177, 208, 242 and 255; Pigment Yellow 138, 139, 150, 185; Pigment Green 7, 36, 58; C.I. CI pigment violet 23; C.I. One or more selected from the group consisting of I Pigment Blue 15: 3 and 15: 6 is used.

  The pigment is preferably contained in an amount of 5 to 60% by weight, more preferably 10 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the pigment is contained in an amount of 5 to 60% by weight, the color density of the pixel is sufficient even when a thin film is formed, and the drop-off property of the non-pixel portion does not deteriorate during development, so that it is preferable that no residue is generated.

  The pigment is preferably a pigment dispersion in which the pigment particle size is uniformly dispersed. Examples of a method for uniformly dispersing the particle size of the pigment include a method of dispersing by adding a pigment dispersant, and the pigment is uniformly dispersed in the solution by the above method. A pigment dispersion can be obtained.

  The pigment dispersant is added to disaggregate the pigment and maintain stability. Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, and polyester. And surfactants such as polyamines can be used, and these can be used alone or in combination of two or more.

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

  Specific examples of the anionic surfactant 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, and dodecylbenzenesulfonic acid. And alkylaryl sulfonates such as sodium and sodium dodecylnaphthalene sulfonate.

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

  Other examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.

  The pigment dispersant preferably contains an acrylate dispersant (hereinafter referred to as an acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150, and the acrylate dispersants may be used alone or in combination of two or more. Can be used in combination.

  As the pigment dispersant, other resin type pigment dispersants may be used in addition to the acrylate dispersant. Examples of the other resin-type pigment dispersants include known resin-type pigment dispersants, particularly polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylates, and polycarboxylates (partially ) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids and their modified products, or free ( free) The same oily dispersant as the amide formed by the reaction of a polyester having a carboxyl group and poly (lower alkyleneimine) or a salt thereof; (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) Acrylate ester Polymers, styrene-maleic acid copolymers, water-soluble resins or water-soluble polymer compounds such as polyvinyl alcohol or polyvinyl pyrrolidone; polyesters; modified polyacrylates; addition products of ethylene oxide / propylene oxide; phosphate esters it can.

  As a commercial product of the pigment dispersant of the other resin type, as the cationic resin dispersant, for example, trade names of BYK Chemical Co., Ltd .: 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 Corporation trade 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, EFK -4510, EFKA-4800; trade names of Lubilzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T -8000; Ajinomoto brand names: AJISPUR PB-821, Ajisper PB-822, Azisper PB-823; Kyoeisha Chemical brand names: FLORENE DOPA-17HF, FLOREN DOPA-15BHF, FLOREN DOPA- 33, florene DOPA-44, and the like.

  In addition to the acrylate dispersants described above, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate dispersant.

  The pigment dispersant is preferably contained in an amount of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment. When the content of the pigment dispersant exceeds 60 parts by weight, the viscosity increases. When the content is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion. is there.

  The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye that has a solubility in an organic solvent and can ensure the solubility in an alkali developer, and the reliability such as heat resistance and solvent resistance.

  As the dye, an acid dye having an acid group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide system of an acid dye, or a derivative thereof can be used. In addition, azo, xanthene, and phthalocyanine acid dyes and derivatives thereof may be selected. Preferably, the dye may be a compound classified as a dye in a color index (published by The Society of Dyers and Colorists) or a known dye described in a dye note (Color Dye).

Specific examples of the dye include C.I. I. As solvent dye,
C. I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179;
C. I. Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;
C. I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49;
C. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162;
C. I. Solvent Orange 2, 7, 11, 15, 26 and 56;
C. I. Mention may be made of dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

  C. above. I. Among solvent dyes, C.I. I. Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179; I. Solvent Blue 35, 36, 44, 45 and 70; C.I. I. Solvent Violet 13 is preferred, and C.I. I. Solvent red 8, 122 and 132 are more preferred.

In addition, C.I. I. As an acid dye, C.I. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;
C. I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 335 and 340;
C. I. Acid Violet 6B, 7, 9, 17, 19, and 66;
C. I. And dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, and 109.

  C. above. I. Among acid dyes, C.I. I. Acid Red 92; I. Acid Blue 80, 90; and C.I. I. Acid Violet 60 is preferable because of its excellent solubility in organic solvents.

In addition, C.I. I. As a direct dye
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138 and 141;
C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;
C. I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190,192,193,194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;
C. I. Dyes such as direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82 can be mentioned.

In addition, C.I. I. As a mold dye,
C. I. Moldant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;
C. I. Moldand Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;
C. I. Moldand Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;
C. I. Moldant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83 and 84;
C. I. Moldan violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;
C. I. Mention may be made of dyes such as Moldant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

  The dyes can be used alone or in combination of two or more.

  The content of the dye in the colorant is preferably 0.5 to 80% by weight, more preferably 0.5 to 70% by weight, and 1 to 70% by weight based on the total solid content of the colorant. Further preferred. When the dye content of the colorant is 0.5 to 80% by weight, it is possible to prevent the problem of lowering the reliability of the dye coming out of the organic solvent after pattern formation, and the sensitivity is improved.

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

  The content of the colorant is preferably 5 to 60% by weight, more preferably 10 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the colorant is contained in the amount of 5 to 60% by weight, the color density of the pixel is sufficient when a thin film is formed, and the drop-out property of the non-pixel portion does not deteriorate during development, so that the residue hardly occurs. There is.

The additive additive can be selectively added to the colored photosensitive resin composition of the present invention as necessary. For example, other polymer compound, curing agent, surfactant, adhesion promoter, oxidation agent One or more selected from the group consisting of an inhibitor, an ultraviolet absorber and an aggregation inhibitor can 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 curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

  Specific examples of the epoxy compound in the curing agent include bisphenol A 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 other aromatics. Aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of the above epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, alicyclic or aromatic epoxies Examples thereof include a compound, a butadiene (co) polymer epoxy compound, an isoprene (co) polymer epoxy compound, a glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.

  Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylate bisoxetane.

  The curing agent can 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 together with the curing agent.

  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 utilized for the said polyhydric carboxylic acid anhydrides. Examples of the commercially available products include ADEKA HARDNER, EH-700 (manufactured by ADEKA INDUSTRY CO., LTD.), RIKACID HH (manufactured by Shin Nippon Rika Co., Ltd.), MH-700 (manufactured by Nippon Nippon Rika Co., Ltd.), and the like. it can. The curing agents exemplified above can be used alone or in admixture of two or more.

  The surfactant can be used to further improve the film formation of the colored photosensitive resin composition, and is based on silicone, fluorine, ester, cation, anion, nonionic, and amphoteric surfactants. An agent or the like can be preferably used.

  Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone, Inc. as commercially available products, and TSF-4440, TSF-4300, TSF-4445, and TSF manufactured by GE Toshiba Silicone. -4446, TSF-4460 and TSF-4442.

  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.

  Other commercially available products include KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW) (Kyoeisha Chemical Co., Ltd.), FTOP (EFTOP) (Tochem Products), MegaFac (MEGAFAC) (Dainippon Ink Chemical Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) ), EFKA (EFKA Chemicals), PB 821 (Ajinomoto Co., Inc.), Disperbyk-series (BYK-chemi), and the like.

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

The kind of the adhesion promoter is not particularly limited, and specific examples of the adhesion promoter that can be used include pinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and 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- Mercaptopropyltrimeth Shishiran, 3 isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane and the like.
The adhesion promoters exemplified above can be used alone or in combination of two or more.
The adhesion promoter is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

  The kind of the antioxidant is not particularly limited, and examples thereof include 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like. Can do.

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

  The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate.

  It is preferable that the additive may be included at 0.1 to 5% by weight with respect to 100% by weight of the whole colored photosensitive resin composition. When the additive is included within the above range with respect to the colored photosensitive resin composition, the purpose of each additive is not reducing the performance of the color filter produced with the colored photosensitive resin composition. There is an advantage that performance can be imparted.

  The colored photosensitive resin composition of the present invention can be produced, for example, as follows.

  First, the pigment of the colorant is mixed with a solvent and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, if necessary, a pigment dispersant, a part or all of the alkali-soluble resin, or a dye can be mixed with a solvent and dissolved or dispersed.

  The mixed dispersion is further added with a dye, the remaining alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and, if necessary, an additive and a solvent so as to have a predetermined concentration. Although the colored photosensitive resin composition which concerns can be manufactured, it is not limited to these.

The present invention provides a color filter produced from the colored photosensitive resin composition and an image display device including the color filter.

  Examples of the image display device that can include such a color filter include, but are not limited to, a liquid crystal display device, an OLED, a flexible display, and the like. An image display device can be exemplified.

  The color filter can be produced by applying the above-described colored photosensitive resin composition of the present invention on a substrate, photocuring and developing to form a pattern.

  First, a chromatic component such as a solvent is removed by applying a colored photosensitive resin composition to a substrate and then drying by heating to obtain a smooth coating film.

As the coating method, for example, spin coating, casting coating method, roll coating method, slit and spin coating, or slit coating method can be used. After application, it is heated and dried (pre-baked), or heated after drying under reduced pressure to volatilize volatile components such as a solvent.
Here, the heating temperature is preferably 0 to 200 ° C, more preferably 80 to 130 ° C. The coating thickness after heat drying is usually about 1 to 8 μm. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming 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 substrate are accurately aligned. When the ultraviolet ray is irradiated, the portion irradiated with the ultraviolet ray is cured.

  As the ultraviolet rays, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like can be used. The irradiation amount of ultraviolet rays can be appropriately selected as necessary, and is not particularly limited in the present invention. If the cured coating film is brought into contact with a developer to dissolve the non-exposed portion and developed, the desired pattern shape can be formed.

As the developing method, any of a liquid addition method, a dipping method, a spray method and the like may be used. Further, the substrate may be tilted at an arbitrary angle during development. The developer 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, sodium silicate, silicic acid. Examples include potassium, 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 can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably from 0.01 to 10% by weight, more preferably from 0.03 to 5% by weight.

  As the surfactant in the alkaline developer, at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and a cationic surfactant can be used.

  Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene block copolymers. Sorbitan fatty acid 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 lauryl alcohol sulfuric acid, higher alcohol sulfates such as sodium stearate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecylbenzenesulfone. Examples thereof include alkylaryl sulfonates such as sodium acid and sodium dodecylnaphthalene sulfonate.

  Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

  The concentration of the surfactant in the developer is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, and still more preferably 0.1 to 5% by weight. After the development, it is washed with water and, if necessary, post-baking at 150 to 230 ° C. for 10 to 60 minutes can be performed.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, embodiment of this invention disclosed below is only an illustration and the scope of the present invention is not limited to these embodiment. The scope of the present invention is defined in the claims, and includes the meanings equivalent to the description of the claims and all modifications within the scope. Further, “%” and “part” representing the contents in the following examples and comparative examples are based on weight unless otherwise specified.

<Experimental example>

Synthesis Example 1 Production of Alkali-Soluble Resin 100 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether were charged into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. Was replaced with nitrogen from air, 8.2 g of azobisisobutyronitrile, 3.1 g of monomethacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd., FA-513M), 2-ethylhexyl acrylate 55. 2 g, 4-methylstyrene 5.9 g, glycidyl methacrylate 85.2 g, and n-todecanethiol 6.0 g were added. Then, the temperature of the reaction liquid was raised to 80 ° C. with stirring and reacted for 4 hours.

  After lowering the temperature of the reaction solution to room temperature and replacing the atmosphere of the flask with nitrogen to air, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid and 136 g of propylene glycol monomethyl ether acetate were added from the dropping funnel. After dropwise addition over 2 hours, the reaction was carried out at 100 ° C. for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added and reacted at 80 ° C. for 6 hours to obtain an alkali-soluble resin of Synthesis Example 1.

  The alkali-soluble resin of Synthesis Example 1 contains all the structural units of Chemical Formula 1, Chemical Formula 2 and Chemical Formula 4, and the solid content acid value of the alkali-soluble resin is 36.2 mgKOH / g, and the weight measured by GPC The average molecular weight Mw was about 7540.

Synthesis Example 2 Production of Alkali-Soluble Resin 100 g of propylene glycol monomethyl ether acetate and 100 g of propylene glycol monomethyl ether were charged into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction tube. After the atmosphere was replaced with nitrogen from air, 8.2 g of azobisisobutyronitrile, 3.1 g of monomethacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd., FA-513M), 38.4 g of n-butyl acrylate , 4-methylstyrene 5.9 g, glycidyl methacrylate 85.2 g, and n-todecanethiol 6.0 g. Then, the temperature of the reaction liquid was raised to 80 ° C. with stirring and reacted for 4 hours.

  The temperature of the reaction solution was lowered to room temperature, and the atmosphere of the flask was replaced with nitrogen. Then, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol, 43.2 g of acrylic acid and 136 g of propylene glycol monomethyl ether acetate were added from the dropping funnel. After dripping over time, it reacted at 100 degreeC for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 g of succinic anhydride was added, and the reaction was carried out at 80 ° C. for 6 hours.

  The alkali-soluble resin of Synthesis Example 2 contains all the structural units of Chemical Formula 1, Chemical Formula 2, and Chemical Formula 4, and the solid content acid value of the alkali-soluble resin is 42.3 mgKOH / g, measured by GPC The weight average molecular weight Mw was about 6020.

Synthesis Example 3 Production of Alkali-Soluble Resin 182 g of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. After the replacement, the temperature was raised to 100 ° C.

  Thereafter, 70.5 g of benzyl methacrylate, 43.0 g of methacrylic acid, 22.0 g of monomethacrylate having a tricyclodecane skeleton (manufactured by Hitachi Chemical Co., Ltd., FA-513M), 136 g of propylene glycol monomethyl ether acetate, and azobis were added to the flask. The mixed solution in which 3.6 g of isobutyronitrile was mixed was dropped into the flask over 2 hours from the dropping funnel, and stirring was continued at 100 ° C. for 5 hours.

Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were put into the flask and reacted at 110 ° C. for 6 hours. .
The alkali-soluble resin of Synthesis Example 3 contains only the structural unit of Chemical Formula 1, the solid content acid value of the alkali-soluble resin was 79 mgKOH / g, and the weight average molecular weight Mw measured by GPC was 13000. .

Synthesis Example 4: Synthesis of photopolymerization initiator (C-1)
Reaction 1.
A solution in which 5.0 g of 2-nitroflorene is dissolved in 100 ml of anhydrous nitrobenzene and 6.31 g of anhydrous aluminum chloride is added, then the reaction is heated to 45 ° C., and 2.79 g of acetyl chloride is dissolved in 30 ml of anhydrous nitrobenzene. Was slowly added over 30 minutes and the reaction was warmed to 65 ° C. and stirred for 1 hour. Thereafter, the reaction product was cooled to room temperature, 70 ml of distilled water was added and stirred for about 30 minutes, and then the product was filtered. The obtained solid product was dispersed in 50 ml of ether, stirred at room temperature for 30 minutes, filtered and dried to give a pale yellow reactant 1 (1- (9,9-H-7-nitrofloren-2-yl). -Ethanone) 5.08 g was obtained.

Reaction 2.
After 1.5 g of the reaction product 1 was dispersed in 30 ml of ethanol and 0.49 g of hydroxylamine hydrochloride and 0.58 g of sodium acetate were added, the reaction solution was gradually heated and refluxed for 2 hours. The reaction product was cooled to room temperature, 20 ml of distilled water was added, and the resulting solid product was stirred for about 30 minutes, filtered, washed with distilled water many times, and dried to a pale gray reaction product. 1.38 g of 2 (1- (9,9-H-7-nitrofloren-2-yl) -ethaneone oxime) was obtained.

Reaction 3.
After 1.20 g of the reaction product 2 was dispersed in 50 ml of ethyl acetate and 0.69 g of acetic anhydride was added, the reaction solution was gradually heated and refluxed for 3 hours. The reaction product was cooled to room temperature and washed in the order of 20 ml of saturated aqueous sodium hydrogen carbonate solution and 20 ml of distilled water, and then the collected organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure to obtain the product obtained. Recrystallization from 20 ml of methanol gave 1.22 g of pale yellow initiator C-1 (1- (9,9-H-7-nitrofloren-2-yl) -ethaneonoxime-O-acetate). .

Synthesis Example 5: Synthesis of photopolymerization initiator (C-2)
Reaction 1.
200.0 g of fluorene, 268.8 g of potassium hydroxide, and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl sulfoxide under a nitrogen atmosphere to maintain the reaction at 15 ° C., and then 283.3 g of bromoethane was added over 2 hours. The reaction was stirred slowly at 15 ° C. for 1 hour. Thereafter, 2 L of distilled water was added to the reaction and stirred for 30 minutes, and then the product was extracted with 2 L of dichloromethane. The extracted organic layer was washed twice with 2 L of distilled water, and then the recovered organic layer was dried over anhydrous magnesium sulfate. The product obtained by drying under reduced pressure and distilling off the solvent under reduced pressure was subjected to fractional distillation under reduced pressure to obtain 248.6 g of a pale yellow reactant 1 (9,9-diethyl-9H-fluorene) as a highly viscous liquid. Obtained.

Reaction 2.
After dissolving 100.5 g of the reaction product 1 in 1 L of dichloromethane and cooling the reaction product to −5 ° C., slowly adding 72.3 g of aluminum chloride, and taking care not to raise the temperature of the reaction water, 50 ml of dichloromethane 50.1 g of diluted propionyl chloride was slowly added over 2 hours and the reaction was stirred at −5 ° C. for 1 hour. Thereafter, the reaction product is slowly poured into 1 L of ice water and stirred for 30 minutes to separate the organic layer. The organic layer recovered by washing with 500 ml of distilled water is distilled under reduced pressure, and the obtained product is subjected to silica gel column chromatography. (Developing solvent; ethyl acetate: n-hexane = 1: 4) and purified by the reaction product 2 (1- (9,9-diethyl-9H-fluoren-2-yl) -1- Propanone) 75.8g was obtained.

Reaction 3.
44.5 g of reactant 2 was dissolved in 900 ml of tetrahydrofuran (THF), 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrous acid were added in that order, and the reaction was stirred at 25 ° C. for 6 hours. . Then, 500 ml of ethyl acetate was added to the reaction solution and stirred for 30 minutes to separate the organic layer. After washing with 600 ml of distilled water, the collected organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. The obtained solid product was recrystallized using 300 ml of a mixed solvent of ethyl acetate: hexane (1: 6) and then dried to form a reaction product 3 (1- (9,9- Diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime) 27.5 g was obtained.

Reaction 4
The reactant 3 was dissolved in 1 L of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere to maintain the reactant at −5 ° C., then 35.4 g of triethylamine was added and the reaction solution was stirred for 30 minutes. Thereafter, a solution prepared by dissolving 27.5 g of acetyl chloride in 75 ml of N-methyl-2-pyrrolidinone was slowly added over 30 minutes, and the reaction was stirred for 30 minutes, taking care not to raise the temperature. Thereafter, 1 L of distilled water was slowly added to the reaction product and stirred for 30 minutes to separate the organic layer. The collected organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled under reduced pressure. The resulting solid product was recrystallized using 1 L of ethanol and then dried to give initiator C-2 (1- (9,9-diethyl-9H-fluorene-2) as a pale gray solid. -Il) -1,2-propanedione-2-oxime-O-acetate) 93.7 g.

Examples 1 to 6 and Comparative Examples 1 to 6: Production of colored photosensitive resin composition Colored photosensitive resin compositions were produced using the components and contents (unit: wt%) shown in Table 1 below.

Production Example 1 Pigment dispersion composition (D) C.I. I. Pigment Blue 15: 6 is 12.5 parts by weight, DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, 7.5 parts by weight, and C.I. I. Pigment Acid Red 52 (1.2 parts by weight), propylene glycol methyl ether acetate (72 parts by weight) as a solvent, and propylene glycol monomethyl ether (8 parts by weight) were mixed and dispersed by a bead mill for 12 hours to prepare Pigment Dispersion Composition D .

<Test method>

Experimental Example 1: Evaluation of applicability The discharge experiment of the colored photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 6 was performed using SHOT mini 200s manufactured by MUSASI. Specifically, the colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were applied with a head speed of 250 mm / s at a constant pressure to produce a 15-inch square glass substrate (manufactured by Corning, The coating properties were evaluated by discharging 10 cm × 10 times on “EAGLE XG”).

The evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.
◎: Out of discharge: None ○: Out of discharge: 1 to less than 3 times △: Out of discharge: 3 to less than 10 times ×: Out of discharge: 10 times or more

Experimental Example 2: Evaluation of development speed, adhesion and sensitivity Each of the colored photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 6 was spin-coated by a 2-inch square glass substrate (manufactured by Corning, “EAGLE XG ”), 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 test photomask having a pattern in which the transmittance is changed stepwise in the range of 1 to 100% and a line / space pattern of 1 μm to 100 μm is placed on the thin film, and the distance from the test photomask is 300 μm. Then, ultraviolet rays were irradiated. At this time, the ultraviolet light source is irradiated with an illuminance of 60 mJ / cm ² using a 1 kW high-pressure mercury lamp including all of g, h, and i rays, and no optical filter is used. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes. The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C. for 25 minutes to produce each color filter. The film thickness of the color filter manufactured above was 2.4 μm.

  In the development process in the above process, the time (development speed) required until the non-exposed part was completely dissolved in the developer was measured and shown in Table 2 below.

Further, the generated pattern was observed with an optical microscope, the degree of discontinuity of the 20 μm pattern was evaluated according to the following criteria, and the adhesion evaluation results are shown in Table 2 below.
○: Pattern break: None △: Pattern break: 1-4
×: Pattern interruption: 5 or more

  In addition, for sensitivity evaluation, the pixel portion obtained as described above was observed to observe whether there was surface roughness under NaLamp, which is shown in FIG.

  In FIG. 1, the left part is a part with surface roughness, and the right part is a part without surface roughness.

The minimum required exposure (mJ / cm ² ) for forming a pattern having no surface roughness was measured and is shown in Table 2 below.

  As can be seen from Table 2, in Examples 1 to 6 using the colored photosensitive resin composition according to the present invention, it was found that all of coating property, developing speed, adhesion and sensitivity were excellent.

Claims (8)

An alkali-soluble resin; comprising a photopolymerizable compound and a photopolymerization initiator;
The alkali-soluble resin includes a structural unit represented by the following chemical formula 1 and a structural unit represented by the chemical formula 2,
The photopolymerization initiator includes a colored photosensitive resin composition containing a compound represented by the following chemical formula 3:
[Chemical Formula 1]
[Chemical formula 2]
[Chemical formula 3]
In Formula 1,
R1 is hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms with or without heteroatoms, or an aromatic hydrocarbon having 6 to 12 carbon atoms with or without heteroatoms;
n is an integer of 1 to 500;
In Formula 2,
R2 is hydrogen or an alkyl group having 1 to 12 carbon atoms,
R3 is a linear alkyl group having 2 to 20 carbon atoms or a branched alkyl group having 2 to 20 carbon atoms,
m is an integer from 1 to 500;
In Formula 3,
R4 to R7 are each independently hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,
R8 to R14 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an amino group, a nitro group, a cyano group, or a hydroxy group,
p is 0 or 1. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin further includes a structural unit represented by the following chemical formula 4:
[Chemical formula 4]
In Formula 4,
R15 and R17 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms,
R16 is a residue containing a carboxylic acid derived from an acid anhydride;
q is an integer of 1 to 500.   The acid anhydride is phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, methyl succinic anhydride, 3,3-dimethyl glutaric anhydride, phenyl succinic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimethyl anhydride, hexahydrophthalic anhydride and carb anhydride The colored photosensitive resin composition of Claim 2 containing 1 or more types selected from the group which consists of a thing.   The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is contained in an amount of 10 to 80% by weight based on the total solid content of the colored photosensitive resin composition.   2. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is contained in an amount of 0.1 to 10 wt% with respect to the entire colored photosensitive resin composition.   The colored photosensitive resin composition according to claim 1, further comprising a solvent and a colorant.   The color filter containing the hardened | cured material of the coloring photosensitive resin composition as described in any one of Claims 1-6.   An image display device comprising the color filter according to claim 7.