KR20190110230A - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition capable of preventing a hole from being generated in a pattern, a color filter including the same and an image display device. The colored photosensitive resin composition of the present invention comprises a photopolymerization initiator (A) including a photopolymerization initiator (a1) having a light absorption rate of 0.1% or more at a wavelength of 365 nm.

Description

Colored photosensitive resin composition, a color filter and an image display apparatus including the same {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND IMAGE DISPLAY DEVICE USING THE SAME}

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

A method of forming a color filter using a colored photosensitive resin composition, wherein a coating film of a colored photosensitive resin composition is formed on a substrate or a substrate on which a light shielding layer having a desired pattern is formed in advance, and light is passed through a photomask having a predetermined pattern. The method of obtaining the pixel of each color is mainly used by irradiation (henceforth an exposure), developing, dissolving and removing an unexposed part, and post-baking after that.

In addition, in recent years, the technical field of color filters aims to shorten the exposure time by reducing the exposure amount, and in order to meet the demand for high color purity of an image display device, which is required in recent years, the content of the colorant in the colored photosensitive resin composition (Ratio) is increasing, which may cause problems such as decreased adhesion and residues when the color filter is manufactured while the content of components other than colorants is reduced.

In this regard, Korean Patent No. 10-0875269 includes an alkali-soluble resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent, wherein the alkali-soluble resin comprises a) at least one double bond represented by a specific chemical formula. Ethylenically unsaturated monomers comprising; b) ethylenically unsaturated monomers having at least one carboxyl group; And c) a copolymer with an ethylenically unsaturated monomer capable of copolymerizing with the monomer of b), which is excellent in adhesion without residue and can produce a high resolution color filter made of ultra fine pixels. Although the photosensitive resin composition and the color filter using the same have been described, the shape of the pattern is formed in the form of an inverted tape before the post-heat treatment process (post bake) when the color filter is manufactured using such a composition, so that an error occurs in the process. There is.

Republic of Korea Patent No. 10-0875269 (2018.12.15.)

The present invention is to solve the above problems, before the post-baking process belonging to the high heat treatment of the color filter manufacturing process can be formed in the form of a pure tapered color photosensitive resin that does not cause a problem in the process It is an object of the present invention to provide a composition, a color filter comprising the same, and an image display device.

The colored photosensitive resin composition of this invention for achieving the said objective contains a photoinitiator (A), The said photoinitiator (A) contains the photoinitiator (a1) whose light absorption in 365 nm wavelength is 0.1% or more, The said The photopolymerization initiator (a1) is characterized in that the compound represented by the following formula (1) or formula (2):

[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,

R ₁ are each independently represented by Formula 3,

The molecular weight of R ₂ is each independently 50 to 150,

Each R ₃ is independently a substituted or unsubstituted diphenylsulfide group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted fluorene)

[Formula 3]

(In Chemical Formula 3,

R ₄ is C1 to C8 alkylene group, C6 to C20 arylene group or C7 to C25 arylalkylene group,

Each R ₅ is independently CN, an alkyl group of C 1 to C 8, a structure of a ring of C 3 to C 8, an aryl group of C 6 to C 20, or an arylalkyl group of C 7 to C 25).

Moreover, the color filter of this invention is characterized by including the hardened | cured material of the coloring photosensitive resin composition mentioned above.

In addition, the image display apparatus of the present invention is characterized by including the above-described color filter.

 The colored photosensitive resin composition of the present invention has the advantage that the shape of the pattern before the post-baking process in the color filter manufacturing process can be implemented in the form of a forward taper does not cause problems in the manufacturing process.

The color filter of the present invention has the same advantages as described above.

The image display device of the present invention has the same advantages as described above.

1 to 3 illustrate the manufacturing process of the color filter.

In the present invention, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

In the present invention, when a part is said to "include" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

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

<Coloring Photosensitive Resin Composition>

The colored photosensitive resin composition which concerns on one aspect of this invention contains a photoinitiator (A), The said photoinitiator (A) contains the photoinitiator (a1) whose light absorption in 365 nm wavelength is 0.1% or more, The said photoinitiator (a1) is a compound represented by the following formula (1) or (2), it is possible to implement the form of the pattern in the form of a taper before the post-baking revolution during the color filter manufacturing process, and finished the post-baking It is possible to prevent the occurrence of defects such as light leakage caused by the inverse taper formed in the final result, there is an advantage that can prevent the occurrence of holes (hole) in the formed pattern.

[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,

R ₁ are each independently represented by Formula 3,

The molecular weight of R ₂ is each independently 50 to 150,

Each R ₃ is independently a substituted or unsubstituted diphenylsulfide group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted fluorene)

[Formula 3]

(In Chemical Formula 3,

R ₄ is C1 to C8 alkylene group, C6 to C20 arylene group or C7 to C25 arylalkylene group,

Each R ₅ is independently CN, an alkyl group of C 1 to C 8, a structure of a ring of C 3 to C 8, an aryl group of C 6 to C 20, or an arylalkyl group of C 7 to C 25).

The alkyl group of C1 to C8 includes a straight or branched type, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl or n-octyl and the like.

The C6 to C20 aryl group includes phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.

The arylalkyl group of C7 to C25 includes benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl or cinnamil.

Photopolymerization Initiator (A)

The colored photosensitive resin composition which concerns on one aspect of this invention contains a photoinitiator (A), The said photoinitiator (A) contains the photoinitiator (a1) whose light absorption in 365 nm wavelength is 0.1% or more, The said photoinitiator (a1) is a compound represented by the following formula (1) or (2), it is possible to implement the shape of the pattern in the form of a taper before the post-baking revolution during the color filter manufacturing process, there is a problem during the manufacturing process There is an advantage that can be prevented from occurring, and that a hole can be prevented from occurring in the formed pattern.

The photopolymerization initiator (a1) may be synthesized and used by a person skilled in the art of organic chemistry in a conventional manner, or a commercially available product may be purchased.

The colored photosensitive resin composition which concerns on one Embodiment of this invention may further contain photoinitiator (a2) other than the photoinitiator (a1) mentioned above.

In this case, the photopolymerization initiator (a2) which may be further included is not particularly limited as long as it is capable of polymerizing the alkali-soluble resin and the photopolymerizable compound which may be included together, for example, acetophenone series, benzoin series, benzophenone series, Thioxanthone, triazine, oxime, onium salt, nitrobenzyltosylate or benzointosylate. Preferred acetophenone compounds for the present invention include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-. 1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketones, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, and 2-methyl-2-morpholino-1- (4- Methylthiophenyl) propan-1-one is more preferable. It is also possible to use a plurality of acetophenone-based compounds and other photopolymerization initiators in combination. As photopolymerization initiators other than the acetophenone-based compounds, active radical generators, sensitizers, acid generators and the like that generate active radicals by irradiation with light Can be mentioned. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds or oxime compounds. Examples of the benzoin compounds include benzoin and benzoin methyl ether. , Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like. As a benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thi, for example. Oxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycytoxanthone, etc. are mentioned. As a triazine type compound, it is 2, for example. , 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- (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-di Ethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1 , 3,5-triazine and the like. Examples of oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butane-1,2 -Butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate Ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -ethyl acetate-O-benzoate, etc. are mentioned. Examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. Can be. As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo Acetate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned. In addition, some compounds may simultaneously generate active radicals and acids. For example, the triazine-based photopolymerization initiator may be used as an acid generator.

According to one embodiment of the present invention, the content of the photopolymerization initiator (a1) may be included in an amount of 70 to 100 parts by weight based on 100 parts by weight of the total photopolymerization initiator (A) including the same, preferably 90 parts by weight or more. Can be. When the content of the photopolymerization initiator (a1) satisfies the above range, there is an advantage in that the forward taper shape can be better realized.

According to one embodiment of the present invention, the photopolymerization initiator (A) may be included in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total solids in the colored photosensitive resin composition including the same. have. When the content of the photopolymerization initiator (A) is included within the above range, the colored photosensitive resin composition including the same is highly sensitive, and thus the exposure time is shortened, thereby improving productivity and maintaining high resolution.

The coloring photosensitive resin composition of this invention may further contain a photoinitiation start adjuvant. The photopolymerization initiation assistant may be used in combination with a photopolymerization initiator (A), and may be used to promote polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator (A). Examples of the photopolymerization initiation aid include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and the like. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4- Methyl dimethylaminobenzoate, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4 ' -Bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis Preference is given to (diethylamino) benzophenone. As an alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example. Etc. can be mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned. Said photopolymerization start adjuvant can be used individually or in combination of 2 or more types.

In addition, a commercially available product may be used as the photopolymerization start adjuvant, and commercially available photopolymerization start adjuvant includes, for example, EAB-F (product of Hodoga Yagaku Kogyo Co., Ltd.). As a combination of the photoinitiator and photoinitiator adjuvant which are preferable for the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- 2-morpholino-1 -(4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-phenylpropan-1-one / 4,4'-bis (Diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzo Phenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 Oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis Combinations of (diethylamino) benzophenone and the like, and more preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-ratio. There is a combination of s (diethylamino) benzophenone. When the photopolymerization initiator (A) and the photopolymerization initiation aid are used together as described above, the photopolymerization initiation assistant is preferably used in an amount of 10 mol or less per mole of the photopolymerization initiator (A), more preferably 0.01 to 5 mol. Can be.

The coloring photosensitive resin composition according to one embodiment of the present invention may further include at least one selected from the group consisting of alkali-soluble resins, photopolymerizable compounds, colorants, solvents and additives in addition to the photopolymerization initiator (A) described above.

Alkali soluble resin

As said alkali-soluble resin, the copolymer etc. with a carboxyl group-containing monomer and the other monomer copolymerizable with the said carboxyl group-containing monomer are mentioned, for example.

As said carboxyl group-containing monomer, For example, unsaturated monocarboxylic acid, unsaturated carboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, etc. are mentioned. Can be mentioned. Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. Can be. The said carboxyl group-containing monomer can be used individually or in mixture of 2 or more types, respectively.

As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, ethylenically unsaturated monomer containing a double bond, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m Aromatic vinyl compounds such as vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicy Unsaturated carboxyl such as clopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate and glycerol monomethacrylate Acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; Unsaturated ethers, such as vinylmethyl ether, vinyl ethyl ether, and allyl glycidyl ether; Acrylonitrile, methacrylonitrile, (alpha)- Vinyl cyanide compounds such as chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macromonomers; and the like. These monomers can be used individually or in mixture of 2 or more types, respectively.

The content of the carboxyl group-containing monomer unit in the alkali-soluble resin may be 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight, in terms of mass fraction. . When content of a carboxyl group-containing monomeric unit is contained in the said range, solubility to a developing solution is favorable and the pattern at the time of image development can be formed correctly.

As said alkali-soluble resin, a (meth) acrylic acid / methyl (meth) acrylate copolymer, a (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth), for example ) Acrylic / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy ) / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide Copolymer, (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer, etc. are mentioned.

Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / Methyl (meth) acrylate / styrene copolymer can be preferably used.

As used herein, (meth) acrylate means acrylate and / or methacrylate.

According to one embodiment of the invention, the alkali-soluble resin may have an acid value of 20 to 200 (mgKOH / g). When the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development, thereby improving the film remaining ratio. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

Further, according to one embodiment of the present invention, the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) of the alkali-soluble resin. May be 3,000 to 200,000, preferably 5,000 to 100,000. When the weight average molecular weight is in the above range, the hardness can be improved, the residual film ratio can be improved, and the solubility of the non-exposed part in the developing solution can be improved so that the resolution can be excellent.

According to one embodiment of the present invention, the alkali-soluble resin may be included in an amount of 10 to 80 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the total solids in the colored photosensitive resin composition including the same. When the content of the alkali-soluble resin is included in the above range, the pattern can be formed, the resolution and the residual film ratio can be improved.

Photopolymerizable  compound

The photopolymerizable compound is not particularly limited in the present invention as long as it is a compound that can be polymerized by an active radical, an acid, etc. generated from the photopolymerization initiator by irradiation of light, and is monofunctional, bifunctional, trifunctional or more depending on the number of functional groups. And polyfunctional polymerizable compounds.

Specific examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-. Vinylpyrrolidone, etc. are mentioned.

Specific examples of the bifunctional polymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di ( Meta) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy The late neopentyl glycol diacrylate, the propyl oxylate neopentyl glycol diacrylate, etc. are mentioned.

Specific examples of the trifunctional or higher polyfunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, and propyloxylate trimethyl. Trifunctional polymerizable compounds such as all propane tri (meth) acrylate, glycerylpropyl oxylate triacrylate, and isocyanurate triarylate; Tetrafunctional polymerizable compounds, such as pentaerythritol tetra (meth) acrylate and dimethylol propane tetra (methyl) acrylate; 5-functional polymerizable compounds, such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, the photopolymerizable compounds may be used alone or in combination of two or more thereof. Specifically, a bifunctional or higher polyfunctional polymerizable compound may be preferably used, and in particular, a polyfunctional or higher polyfunctional polymerizable compound is preferable. It may be used, but is not limited thereto.

According to one embodiment of the present invention, the photopolymerizable compound may be included in an amount of 5 to 50 parts by weight, preferably 7 to 45 parts by weight, based on 100 parts by weight of the total solids in the colored photosensitive resin composition including the same. When the photopolymerizable compound is included in the range, there is an advantage that the intensity or smoothness of the pixel portion may be improved.

coloring agent

The colorant is a configuration that can be variously applied according to the use of the color filter, and the kind thereof is not particularly limited in the present invention.

The colorant may be any one of a pigment, a dye, or a natural dye, and as the pigment, a compound classified as pigment in the Color Index (Published by The Society of Dyers and Colourists) may be used. As the colorant of the present invention, an organic pigment may be preferable in view of excellent heat resistance and color development.

Specific examples of preferred pigments that can be used in the present invention are

C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 194, C.I. Yellow pigments such as pigment yellow 214;

Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Orange pigments such as pigment orange 73;

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Red pigments such as Pigment Red 264 and C.I. Pigment Red 265;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigments such as pigment blue 60 and the like;

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Violet pigments such as pigment violet 38;

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as pigment green 58;

C.I. Pigment Brown 23, C.I. Brown pigments such as pigment brown 25;

C.I. Pigment Black 1, C.I. Black pigments, such as pigment black 7, etc. are mentioned.

Among these, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6 and C.I. It may be desirable to include one or more pigments selected from pigment green 36.

The above organic pigments and inorganic pigments may be used alone or in combination of two or more kinds thereof. For example, in forming a red pixel, C.I. Pigment Red 254 and C.I. Pigment yellow 139 containing C.I. Pigment Green 58, C.I. Pigment Yellow 150 or C.I. Containing pigment yellow 138; forming a blue pixel is C.I. Containing Pigment Blue 15: 6 may be preferred for enhancing color reproduction, respectively, but is not limited thereto.

The dye may be used at least one type without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer. The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected. Examples of the dye include compounds classified as dyes in the color index (Published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (color dyeing yarn).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Red dyes such as solvent red 8, 45, 49, 122, 125 and 130;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 45, 56, 62 and the like;

C.I. Blue dyes such as solvent blue 35, 37, 45, 59, 67 and the like;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

See also C.I. As an acid dye

CI 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 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 ;

CI 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, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as, 382, 383, 394, 401, 412, 417, 418, 422, 426;

Orange dyes such as C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI 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 Blue dyes such as, 335 and 340;

Violet dyes such as C.I. acid violet 6B, 7, 9, 17, 19 and the like;

Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.

Also as a C.I. direct dye

CI 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 Yellow dyes such as, 136, 138, and 141;

CI 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 Red dyes such as, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

Orange dyes such as C.I.direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;

Violet dyes such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like;

Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

In addition, C.I. As modanto dye

Yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;

CI Modanto Orange Orange such as 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dyes;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, Blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;

Violet dyes such as C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like;

Green dyes, such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.

The colorant is preferably contained in 10 to 70 parts by weight, preferably 20 to 60 parts by weight based on 100 parts by weight of the total solids in the coloring photosensitive resin composition comprising the same. When the content of the colorant is included in the above range, it is possible to form a pattern having a sufficient color density and sufficient mechanical strength when made of a color filter.

Solid content of a coloring photosensitive composition in this invention means the sum total of the component which removed the solvent.

Among the pigments, organic pigments may be subjected to surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, graft treatment of the surface of the pigment with a polymer compound, atomization treatment by sulfuric acid atomization, or impurities. A washing treatment with an organic solvent or water for removal, a removal treatment by an ion exchange method of ionic impurities, or the like can be performed. It is preferable that a colorant is uniform particle size. When the coloring agent is a pigment, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in solution can be obtained by containing a pigment dispersant and performing a dispersion process.

It is preferable to use the said pigment in the form of the pigment dispersion liquid whose particle diameter was disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and these may be used alone or in combination of two or more.

The pigment dispersant is added to maintain the stability of the pigment and deagglomeration can be used without limitation to those commonly used in the art. It may be desirable to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) preferably comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as shown in Korean Patent Laid-Open Publication No. 2004-0014311. As a commercial product of the acrylate-based dispersant manufactured by the living control method, DISPER BYK -2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and the like, but are not limited thereto.

These can be used individually or in combination of 2 types or more, respectively.

The dispersant may use a pigment dispersant of another resin type in addition to the acrylic dispersant described above. The other resin type pigment dispersant is a (partial) of known resin type pigment dispersants, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; And adducts of ethylene oxide / propylene oxide, phosphate esters, and the like. As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (Big) Chemi Corporation: 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 brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned. In addition to the acrylic dispersant described above, pigment dispersants of other resin types may be used alone or in combination of two or more thereof, or may be used in combination with acrylic dispersion.

When the colored photosensitive resin composition further includes a pigment dispersant, the content may be preferably 1 part by weight or less, and more preferably 0.05 part by weight or more and 0.5 part by weight or less per 1 part by weight of the colorant included. When the amount of the pigment dispersant used is within the above range, a pigment in a uniform dispersed state can be obtained.

solvent

The solvent of the present invention can be used without particular limitation so long as it is effective for dispersing or dissolving the other constituents included therein. For example, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferable. Can be used.

As said ether, For example, tetrahydrofuran, tetrahydropyran, 1, 4- dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate Methoxybutyl And the like lactate, methoxy pentyl acetate, anisole, phenetole or methyl anisole.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and the like. Can be.

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate and alkyl esters. Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxyacetic acid methyl, ethoxyacetate, methyl 3-oxypropionate , Ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxy Propyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl lopionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate or γ-butyro Lactone, etc. are mentioned.

As said amides, N, N-dimethylformamide, N, N-dimethylacetamide, etc. are mentioned, for example.

As another solvent, N-methylpyrrolidone, dimethyl sulfoxide, etc. are mentioned, for example.

The aforementioned solvents may be used alone or in combination of two or more thereof. Among them, 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether may be preferably used. The content may be included in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total color photosensitive resin composition including the same. When content of a solvent is the said range, flatness at the time of apply | coating a coloring photosensitive resin composition is favorable, and when a color filter is formed, there exists an advantage that a color density is enough and display property may become favorable.

additive

The colored photosensitive resin composition may further include additives such as an antifoaming agent, a surfactant, a thermal crosslinking agent, an adhesion promoter, an antioxidant, and the like, in order to improve performance, in addition to the aforementioned components.

The surfactant is a component capable of improving the adhesion between the substrate and the colored photosensitive resin composition, and for example, various surfactants such as fluorine-containing surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. Can be used. These can be used individually or in mixture of 2 or more types.

Specific examples of fluorine-containing surfactants include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade name, manufactured by DIC Corporation), FLUORAD FC430, FC431 and FC171 (trade name, product of Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (brand name, the product made by Asahi Glass Co., Ltd.), SOLSPERSE 20000 (brand name, the product made by Lubrizol Japan Limited), etc. are mentioned.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane and trimethylol ethane and their ethoxylates or propoxylates (eg, glycerol propoxylates or glycerine ethoxylates); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, manufactured by BASF) Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester and the like.

Specific examples of cationic surfactants include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), and organo such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Siloxane polymers; (Meth) acrylic acid-based (co) polymers such as POLYFLOW No. 75, No. 90, No. 95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (trade name, manufactured by Yusho Co., Ltd.), and the like. Can be mentioned.

Specific examples of the anionic surfactant include W004, W005, and W017 (trade name, manufactured by Yusho Co., Ltd.).

Specific examples of silicone surfactants include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade name, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 ( Trade names, manufactured by Momentive Performance Materials Inc., KP341, KF6001 and KF6002 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, 323, and 330 (trade name, manufactured by BYK Chemie).

When the thermal crosslinking agent forms a coating film with a colored photosensitive resin composition, the crosslinking reaction may be smoothly generated through UV irradiation and heat treatment, and the component may improve heat resistance. For example, a polyacrylate resin, an epoxy resin, a phenol resin, a melamine resin, an organic acid, an amine compound, an anhydride compound, etc. are mentioned.

The adhesion promoter may improve adhesion to inorganic materials that may be substrates, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, metals such as gold, copper, aluminum, and the like, and taper angle with the substrate. There is an advantage to improve the control ability. For example, a silane coupling agent or a thiol type compound is mentioned, Preferably a silane coupling agent can be used.

The kind of the silane coupling agent is not particularly limited, and specific examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-glycidoxypropylalkyl. Dialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldiakoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxy Cyclohexyl) ethyl trialkoxysilane, vinyl trialkoxysilane, etc. are mentioned, Preferably it is (gamma)-glycidoxy propyl trialkoxysilane or (gamma)-methacryloxypropyl trialkoxysilane, More preferably, it is a gamma-glyciyl silane. Doxypropyltrialkoxysilane. These can be used individually or in mixture of 2 or more types.

Examples of the antioxidant include, generally, 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2,6- Di-sec-butylphenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol, 2-t-octylphenol, 2 , 6-di-t-octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2-t-butyl -p-cresol, 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-o-cresol, 2,6-di-t-dodecylphenol , 2,4-di-t-dodecylphenol, 2-sec-butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec- Butyl-o-cresol, 2-t-octyl-p-cresol, 2-t-dodecyl-p-cresol, 2-t-butyl-6-isopropylphenol, 6-t-octyl-o- Cresol, 6-t-dodecyl-o-cresol, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), octadecyl-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (6-tetra-butyl-3-methylphen ), 4,4'-thio-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propio Nate], 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4 ' -Hydroxyphenyl propionate)] methane and the like, and these may be used alone or in combination of two or more.

The method of preparing the colored photosensitive resin composition of the present invention may be applied without limitation to methods commonly used in the art, but, for example, may be prepared by the following method. The coloring agent is previously mixed with the solvent and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, a pigment dispersant may be used as needed, and some or all of alkali-soluble resin may be mix | blended. The remainder of alkali-soluble resin, a photopolymerizable compound, a photoinitiator, the other components used as needed, and the additional solvent as needed, may further be made into the obtained dispersion liquid (it may be called a mill base hereafter) as needed. By adding and mixing, the desired coloring photosensitive resin composition can be obtained.

<Color filter>

The color filter according to another embodiment of the present invention includes the cured product of the above-described colored photosensitive resin composition, thereby manufacturing the shape of the pattern in the form of a forward taper before the post-baking step in the manufacturing process, thereby preventing problems during the manufacturing process. It is possible to prevent the occurrence of holes in the pattern formation number pattern.

The color filter of the present invention may be manufactured by applying a manufacturing method commonly used in the art without particular limitation, but will be described below with reference to FIGS. 1 to 3.

In order to manufacture a color filter using the colored photosensitive resin composition of the present invention, a colored pattern should be formed. For this purpose, the colored photosensitive resin composition may be patterned. Specifically, referring to FIG. 1, the color layer 11 made of the colored photosensitive resin composition of the present invention is formed on the substrate 10. In this case, the type of the substrate 10 is not particularly limited, and may be a color filter substrate itself, or may be a portion where the color filter is positioned in a display device or the like. The substrate 10 may be a glass plate, a silicon wafer, and a plastic plate such as poly ether sulfate (PES), poly carbonate (PC), or the like. That is, the substrate 10 may be silicon (Si), silicon oxide (SiOx), a glass substrate, or a polymer substrate. Thus, in order to form the color layer 11 which consists of a coloring photosensitive resin composition on the board | substrate 10, the coloring photosensitive resin composition diluted with the solvent, for example, spins, a slit after spin, a slit, a roll, a spray, After coating onto a substrate by a coating method such as an inkjet method, volatile components such as a solvent are volatilized. Thereby, the color layer 11 which consists of a coloring photosensitive resin composition is formed, Comprising: The color layer 11 consists of solid components of a coloring photosensitive resin composition, and contains few volatile components. The thickness of the film surface is determined by the coating conditions such as the viscosity of the composition, the concentration of solids, the coating speed, and the like, and when using the composition of the present invention, a colored layer 11 having a thickness of 0.5 to 5 μm can be obtained.

Next, referring to FIG. 2, the color layer 11 made of the colored photosensitive resin composition is exposed (exposed) to the light 30 on the substrate 10. In order to expose, for example, the color layer 11 is irradiated with light 30 in a predetermined pattern through the photomask 20. At this time, as the light 30, ultraviolet rays g line (wavelength: 436 nm), h line, i line (wavelength: 365 nm) and the like are usually used. Light 30 passes through the pattern of the photomask 20. The photomask 20 provides a light shielding layer for shielding light rays in a predetermined pattern on the surface of the glass plate. Light 30 is shielded by the light shielding layer. The part of the glass plate in which this light shielding layer is not provided is a light transmission part through which light rays pass. According to the pattern of the light transmitting portion, the color layer 11 is exposed. The irradiation amount of light 30 is suitably selected according to the coloring photosensitive resin composition used.

The portion irradiated with the light 30 is much smaller in solubility than the portion without irradiated with light 30, so that the difference in solubility between the two is maximized. For development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As a developer, aqueous solutions, such as an alkali compound, such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide, are used. Referring to FIG. 3, the unirradiated region of the light 30 that is not irradiated by the light 30 of the color layer 11 formed on the substrate 10 is removed by the above phenomenon. On the contrary, the light 30 irradiated region irradiated by the light 30 remains to form the colored pattern 11R. After development, the layer is washed with ordinary water and dried to obtain a predetermined colored pattern 11R. Moreover, you may heat-process after drying. The colored pattern 11R formed by the heat treatment is cured, and the mechanical strength thereof is improved. Thus, since the mechanical strength of the coloring pattern 11R can be improved by heat treatment, it is preferable to use a coloring photosensitive composition containing a curing agent. Heating temperature is usually 180 degreeC or more, Preferably it is 200-250 degreeC.

<Image display device>

The image display apparatus according to still another aspect of the present invention includes the color filter described above, so that a problem does not occur in the manufacturing process and thus there is an advantage in that there is little defect. Specifically, the image display device includes 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 display device for a mobile terminal such as a mobile phone, and a display for a digital camera. Display devices such as devices, display devices for car navigation systems, and the like, and particularly, color display devices may be suitable.

The image display apparatus may include other components that may be normally included in the image display apparatus, such as a light emitting device such as a light source, a light guide plate, a liquid crystal display including a color filter according to the present invention, and the like. Do not.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. Naturally, such modifications and variations fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" indicating contents are by weight unless otherwise specified.

Example  And Comparative example

To prepare a colored photosensitive resin composition by mixing in the configuration and content as shown in Table 1.

Example
One Example
2 Example
3 Example
4 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Colorant ^{1 )} 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 Alkali-soluble resins ^{2 )} 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 Photopolymerizable compound ^{3 )} 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 Photopolymerization initiator A-1 1.0 - - - - - - - A-2 - 1.0 - - - - - - A-3 - - 1.0 - - - - - A-4 - - - 1.0 - - - - A-5 - - - - 1.0 - - - A-6 - - - - - 1.0 - - A-7 - - - - - - 1.0 - A-8 - - - - - - - 1.0 Additives ^{4 )} 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Solvent ^{5 )} 58 58 58 58 58 58 58 58 1) CI Pigment Blue 15: 6
2) Copolymer of methacrylic acid with cyclohexyl methacrylate and benzyl methacrylate (the ratio of methacrylic acid unit, benzyl methacrylate unit and cyclohexyl methacrylate is 20:40:40 in molar ratio, and acid value is 83 , Polystyrene equivalent weight average molecular weight is 13,000)
3) dipentaerythritol hexaacrylate (DPHA, Nippon Gunpowder)
4) Dow Corning Toray Silicone SH8400
5) Propylene Glycol Monomethyl Ether Acetate
A-1: Compound of Formula 4
A-2: Compound of Formula 5
A-3: Compound of Formula 6
A-4: Compound of Formula 7
A-5: compound of formula 8
A-6: compound of formula 9
A-7: OXE-01 (BASF)
A-8: OXE-03 (BASF)

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

Experimental Example  One. Photopolymerization  Absorption rate of initiator and molecular weight measurement of R2

Each photopolymerization initiator used in Examples and Comparative Examples was diluted to 0.001 wt% in propylene glycol monomethyl ether acetate, and absorbed at 365 nm with a UV-VIS Spectrophotometer (Model: UV-2550, manufacturer: SHIMADZU). The measurement results are shown in Table 2 below, and the molecular weights of the moieties corresponding to R ₂ of the general formula (1) or (2) of the present invention in each photopolymerization initiator were calculated and described together.

A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 R ₂ molecular weight 78.1 120.2 98.2 58.1 16.0 178.2 16.0 16.0 Water absorption 0.16 0.15 0.15 0.16 0.15 0.17 0.07 0.22

Referring to Table 2, in the case of the photopolymerization initiators A-1 to A-4 included in the examples in the present invention, the molecular weight of the portion corresponding to R2 and the light absorptivity at a wavelength of 365 nm are included in the range of the present invention. It could be confirmed.

Production Example : Manufacturing of color filter

Each colored photosensitive resin composition prepared in Examples and Comparative Examples was coated on 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. Subsequently, a test photomask having a line / space pattern of 1 μm to 50 μm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated with an illuminance of 50mJ / cm 2 using a 1KW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The UV-irradiated thin film was immersed in a KOH aqueous solution developing solution of pH 10.5 for 1 minute and developed. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 30 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

Experimental Example  2. Pattern Taper ( taper ) shape

The length of the taper before the 220 ° C. heating step in the preparation example was measured by a scanning electron microscope (SEM) as described below, and the results are shown in Table 4 below. At this time, the measuring method of the taper length for distinguishing a forward taper and an inverse taper is as Table 3 below.

Reverse taper (-) Forward taper (+)

Experimental Example  3. Pattern Line width (Sensitivity) evaluation

The line width of the pattern formed in the preparation example was measured using a scanning electron microscope (SEM). When the line width of the pattern was measured to be equal to or larger than the line width (100 µm) of the photomask, the sensitivity of the colored photosensitive resin composition was sufficient, and it was interpreted that the line width was enlarged. At this time, the line width (μm) enlarged compared to the photomask is shown in Table 4 below.

Example
One Example
2 Example
3 Example
4 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Taper Length +1.2 μm +2.1 μm +1.3 μm + 0.5㎛ 3.2 μm Pattern formation impossible 1.2 μm 5.2㎛ Pattern line width (sensitivity) 107㎛ 103㎛ 102 μm 109㎛ 115 ㎛ Pattern formation impossible 102 μm 124㎛

Referring to Table 4, in Examples 1 to 4 that satisfy all of the conditions of the present invention, the sensitivity is superior to those of Comparative Examples 1 to 4 which do not satisfy any of the conditions of the present invention, We confirmed that it can be implemented.

Specifically, in the case of Comparative Examples 1, 2 and 4 using the photopolymerization initiator having a molecular weight of R ₂ outside the range suggested by the present invention, it was confirmed that the shape of the reverse taper was implemented to cause a process defect, in particular, the present invention. In Comparative Example 2 that exceeds the range of the R ₂ molecular weight shown in Figure ₂ it was confirmed that the pattern formation itself is impossible, Comparative Example 3 using a photopolymerization initiator whose absorption at 365nm wavelength does not fall within the range presented in the present invention In the case of the reverse taper shape was implemented, as well as the sensitivity was confirmed that not good.

10: Substrate
11: color layer
11R: Color Pattern
20: photomask
30: light

Claims (10)

It contains a photoinitiator (A),
The photoinitiator (A) comprises a photopolymerization initiator (a1) having a light absorption rate of at least 0.1% at 365 nm wavelength, wherein the photopolymerization initiator (a1) is a compound represented by the following Chemical Formula 1 or Chemical Formula 2 Resin composition:
[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,
R ₁ are each independently represented by Formula 3,
The molecular weight of R ₂ is each independently 50 to 150,
Each R ₃ is independently a substituted or unsubstituted diphenylsulfide group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted fluorene)
[Formula 3]

(In Chemical Formula 3,
R ₄ is C1 to C8 alkylene group, C6 to C20 arylene group or C7 to C25 arylalkylene group,
Each R ₅ is independently CN, an alkyl group of C 1 to C 8, a structure of a ring of C 3 to C 8, an aryl group of C 6 to C 20, or an arylalkyl group of C 7 to C 25). The method of claim 1,
The colored photosensitive resin composition further comprises at least one selected from the group consisting of a photopolymerization initiator (a2), an alkali-soluble resin, a photopolymerizable compound, a solvent and an additive other than the photopolymerization initiator (a1). Composition. The method of claim 1,
The content of the photopolymerization initiator (a1) is a colored photosensitive resin composition, characterized in that it comprises 70 to 100 parts by weight based on 100 parts by weight of the total photopolymerization initiator (A). The method of claim 1,
The photoinitiator (A) is a coloring photosensitive resin composition, characterized in that contained in 0.1 to 30 parts by weight based on 100 parts by weight of the total solid content of the coloring photosensitive resin composition comprising the same. The method of claim 2,
The acid value of the said alkali-soluble resin is 20-200 KOHmg / g, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 2,
The weight average molecular weight of the said alkali-soluble resin is 3,000-200,000, The coloring photosensitive resin composition characterized by the above-mentioned. The method of claim 2,
The alkali-soluble resin is a coloring photosensitive resin composition, characterized in that contained in 10 to 80 parts by weight based on 100 parts by weight of the total solid content of the coloring photosensitive resin composition comprising the same. The method of claim 2,
The photopolymerizable compound is a coloring photosensitive resin composition, characterized in that contained in 5 to 50% by weight based on 100% by weight of the total solid content of the coloring photosensitive resin composition comprising the same. The hardened | cured material of the coloring photosensitive resin composition of any one of Claims 1-8 is contained, The color filter characterized by the above-mentioned. An image display apparatus comprising the color filter of claim 9.

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