JP6868117B2 - Blue photosensitive resin composition, color filter and image display device manufactured using this - Google Patents

Description

The present invention relates to a blue photosensitive resin composition, a color filter and an image display device manufactured by using the blue photosensitive resin composition.

A color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and enables them in minute pixel units, and the size of one pixel is about several tens to several hundreds of micrometers. Is. Such a color filter has a black matrix layer formed in a pattern defined on a transparent substrate to block the boundary portion between each pixel, and a plurality of colors (usually, usually) to form each pixel. It has a structure in which pixel portions in which the three primary colors (red (R), green (G), and blue (B)) are arranged in a predetermined order are laminated in order.

Recently, as one of the methods for realizing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied, but the light emitted from the light source is transmitted through the color filter. There is a problem that a part of the light is absorbed by the color filter and the light efficiency is lowered, and the color reproduction is lowered due to the characteristics of the pigment contained in the color filter.

In order to solve such a problem, a method for manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed.

Specifically, Republic of Korea Published Patent No. 2007-0094679 discloses that color reproducibility can be enhanced by having a color filter layer formed of quantum dots (Quantum Dot), and Republic of Korea Published Patent No. 2009- No. 0036373 discloses that the emission efficiency can be improved and the display quality can be improved by replacing the existing color filter with a light emitting layer made of a quantum dot phosphor.

However, the photosensitive resin composition developed for manufacturing color filters up to now has sufficient requirements such as development speed, excellent pattern characteristics, processability, heat resistance, light resistance, yellowing suppressing effect, and reliability. Did not meet.

INDUSTRIAL APPLICABILITY The present invention is a blue photosensitive color filter capable of realizing a color filter having excellent development speed, excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability, particularly a self-luminous color filter. An object of the present invention is to provide a sex resin composition.

Another object of the present invention is to provide a blue photosensitive resin composition having excellent pattern characteristics and a yellowing suppressing effect.

Furthermore, an object of the present invention is to provide a blue color filter and an image display device manufactured by using the above-mentioned blue photosensitive resin composition.

（前記化学式１において、
Ｒ_１〜Ｒ_４は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基で置換もしくは非置換のフェニル基、炭素数１〜１２のアルキル基で置換もしくは非置換のベンジル基、または炭素数１〜１２のアルキル基で置換もしくは非置換のナフチル基である。）

（前記化学式２において、
Ｒ_５は、水素、炭素数１〜２０のアルキル基、炭素数３〜８のシクロアルキル基、または置換されないか、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基で置換されたフェニル基であるか、

であり、ｎは、１〜４の整数であり、ｍは、１〜６の整数であり；
Ｒ_６は、炭素数１〜８のアルキル基、フェニル基、置換フェニル基、ベンジル基、または置換されたベンジル基；
Ｒ_７は、ジフェニルスルフィド基、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基で置換されたジフェニルスルフィド基、カルバゾール基、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基でカルバゾール基、フルオレン基、または置換されたフルオレン基である。）

（前記化学式３において、
Ｒ_８、Ｒ_９およびＲ_１０は、それぞれ独立に、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’、またはＣＮを示し；
ＲおよびＲ’は、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基、または炭素数２〜２０の複素環基を示し、これらは、ハロゲン原子および／または炭素数２〜２０の複素環基で置換されていてもよいし、これらのうち、アルキル基およびアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合によって中断されていてもよく、また、ＲおよびＲ’は、共に環を形成してもよいし；
Ｙ_１は、酸素原子、硫黄原子、またはセレン原子を示し、ｍは、０〜４の整数を示し、ｐは、０〜５の整数を示し；
ｑは、０または１を示し；
Ｒ_１１、Ｒ_１２、Ｒ_１３およびＲ_１４は、それぞれ独立に、水素原子、ハロゲン原子、または炭素数１〜８のアルキル基を示し；
Ｘ_１は、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基、または炭素数２〜２０の複素環基を示し、これらは、ハロゲン原子および／または炭素数２〜２０の複素環基で置換されていてもよいし、これらのうち、アルキル基およびアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合によって中断されていてもよく；
Ｙ_２およびＹ_３は、それぞれ独立に、酸素原子、硫黄原子、またはセレン原子を示す。）を提供する。 The present invention includes scattered particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The blue photosensitive resin composition, wherein the photoinitiator is at least one selected from the compounds represented by the following chemical formulas 1 to 3.

(In the chemical formula 1,
R _{1 to} R ₄ are independently substituted or unsubstituted with a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It is a naphthyl group substituted or unsubstituted with a benzyl group or an alkyl group having 1 to 12 carbon atoms. )

(In the chemical formula 2,
R ₅ is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or unsubstituted, methyl, methoxy, halogen, carboxyl and phenyl group substituted with a hydroxy group, Is

N is an integer of 1 to 4 and m is an integer of 1 to 6;
R ₆ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group, or a substituted benzyl group;
R ₇ is a diphenyl sulfide group substituted with a diphenyl sulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a carbazole group with a hydroxy group. , A fluorene group, or a substituted fluorene group. )

(In the chemical formula 3,
R ₈ , R ₉ and R ₁₀ independently represent R, OR, COR, SR, CONRR', or CN;
R and R'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogens. It may be substituted with an atomic and / or heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. R and R'may form a ring together;
Y ₁ represents an oxygen atom, a sulfur atom, or a selenium atom, m represents an integer of 0 to 4, and p represents an integer of 0 to 5;
q indicates 0 or 1;
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms;
X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms and. / Or may be substituted with a heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. May;
Y ₂ and Y ₃ independently represent an oxygen atom, a sulfur atom, or a selenium atom. )I will provide a.

The present invention also provides a color filter containing a blue pattern layer made of the above-mentioned blue photosensitive resin composition.

Furthermore, the present invention provides an image display device including the color filter and a light source that emits blue light.

The blue photosensitive resin composition of the present invention contains at least one photoinitiator selected from the compounds represented by chemical formulas 1 to 3 in the blue photosensitive resin composition to increase the development speed. It is possible to realize a color filter having excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability, particularly a self-luminous color filter.

Further, the blue photosensitive resin composition of the present invention contains at least one or more antioxidants selected from phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants. It can provide excellent pattern characteristics and anti-yellowing effect.

Therefore, the blue photosensitive resin composition of the present invention can be usefully used for manufacturing color filters and image display devices.

The blue photosensitive resin composition of the present invention has at least one or more light selected from a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, and compounds represented by chemical formulas 1 to 3. By containing the initiator and the solvent, the blue photosensitive resin composition has excellent development speed and excellent processability, and when formed into a cured film, it has excellent heat resistance and light resistance and excellent reliability. It is possible to realize a color filter, particularly a self-luminous color filter.

Hereinafter, the configuration of the present invention will be described in detail.

Scattered particles The scattered particles of the present invention may be a metal oxide having an average particle size of 10 to 1000 nm, and more preferably in the range of 30 to 300 nm. When the average particle size of the scattered particles satisfies the above range, a sufficient scattering effect of the light emitted from the quantum dots can be expected, and the scattered particles settle or are not uniform in the blue photosensitive composition. The problem of the surface of the light emitting layer is less likely to occur.

The metal oxides include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, It may be an oxide containing one kind of metal selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof. More specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTIO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , It may be one or more selected from the group consisting of SnO, MgO, and combinations thereof. If necessary, materials surface-treated with compounds having unsaturated bonds, such as acrylates, can also be used.

The average particle size and the content of the scattered particles in the overall composition can be appropriately adjusted as necessary so that the emission intensity of the color filter can be sufficiently improved.

The scattered particles may be contained in an amount of 0.1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of the solid content in the blue photosensitive resin. When the content of the scattered particles satisfies the above range, it is possible to reduce the possibility that the problem of reduced stability of the blue photosensitive resin composition occurs while achieving the desired emission intensity.

Blue Colorant In the blue colorant of the present invention, specific examples of the blue pigment include compounds classified as pigments in the color index (The Society of Dyers and Colorists), and more specifically, the blue pigment. Pigments having the following color index (CI) numbers can be mentioned, but are not necessarily limited to these. Specifically, the blue pigment is described in, for example, C.I. I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and the like. I. It is preferable to include one or more selected from the group consisting of Pigment Blue 15: 3, Pigment Blue 15: 6, and Pigment Blue 16.

The blue colorant of the present invention may further contain a blue dye, and as a blue dye, a compound or a dyeing note (color dyeing company) classified as a dye in the Color Index (The Society of Dyers and Colorists). ), The known dyes described in) can be mentioned.

The dyes that can be additionally used are listed.
C. I. As a solvent dye
C. I. Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70 and the like, C.I. I. It is more preferable to contain one or more of Solvent Blue 35, 36, 44, 45 and 70.

In addition, C.I. I. As an acid dye
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 are mentioned, and among them, C.I. I. More preferably, it contains one or more of Acid Blue 80 and 90.

In addition, C.I. I. As a direct dye
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 and the like.

In addition, C.I. I. As a modern dye
C. I. Modant 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 and the like.

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

The blue colorant of the present invention may further contain a purple colorant as an additional colorant. The violet colorant can include one or more of the violet pigments and violet dyes, wherein the violet pigments are specifically C.I. I. Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among others, C.I. I. It is more preferable to include Pigment Violet 23.

Specifically, the purple dye is C.I. I. Solvent Violet, C.I. I. Acid Violet, C.I. I. Direct Violet, C.I. I. Examples include, but are not limited to, modern violet.

Specifically, the above-mentioned C.I. I. Solvent Violet is described in C.I. I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49 and the like, and C.I. I. It is more preferable to include solvent violet 13. C. I. As acid violet, C.I. I. Acid Violet 6B, 7, 9, 17, 19 and 66 and the like can be mentioned. I. More preferably, it contains Acid Violet 66. C. I. As direct violet, C.I. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104 and the like.

In addition, C.I. I. Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58 and the like.

The blue colorant may be contained in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, based on the total weight of the solid content in the blue photosensitive resin. The blue photosensitive resin composition may be contained in an amount of 0.1 to 50% by weight based on 100% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight.

When the content of the blue colorant satisfies the above range, it is advantageous to achieve the effect of suppressing external light reflection, and the problem of lowering the emission intensity or the problem of lowering the viscosity stability of the blue photosensitive resin composition occurs. It is advantageous because it is unlikely.

In the present invention, it is possible to prevent a decrease in the efficiency of blue pixels of a color filter, particularly a self-luminous color filter, by containing a blue colorant and scattered particles even though the blue quantum dots are not contained.

Binder resin The binder resin of the present invention includes a cardo-based binder resin. The cardo-based binder resin has reactivity and alkali solubility due to the action of light and heat, and acts as a dispersion medium for a coloring material. The cardo-based binder resin contained in the blue photosensitive resin composition of the present invention acts as a binder resin for scattered particles and is a resin that can be dissolved in an alkaline developer used in the developing stage for producing a color filter. If so, it is not limited.

The cardo-based binder resin of the present invention may contain one or more of the compounds represented by the chemical formulas 4-1 and 4-2.

であり；
Ｘは、水素原子、炭素数１〜５のアルキル基、または水酸基であり、Ｒ_１９は、水素原子、または炭素数１〜５のアルキル基である。 In the chemical formulas 4-1 and 4-2,
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independent of each other.

Is;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, and R ₁₉ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the present invention, the compound represented by the chemical formula 4-1 is synthesized by the compound represented by the following chemical formula 5-1 and the compound represented by the chemical formula 4-2 is a compound represented by the chemical formula 5-2. May be synthesized using.

The compound represented by the chemical formula 4-1 is at least one of the compounds represented by the chemical formula 6 or the chemical formula 7, and the compound represented by the chemical formula 4-2 is represented by the chemical formula 8 or the chemical formula 9. It may be any one or more of the compounds to be made.

The cardo-based binder resin includes 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene) and 9,9-bis (3-cinnamoil, 4-hydroxyphenyl). Fluorene (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (gycydyl methylate ether) fluorene), 9,9-bis (9,9-bis) 3,4-dihydroxyphenyl) fluorene synamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xanthene) (3) , 6-diggycidyl methyllate ether spiro (fluorene-9,9-xantene), 9,9-bis (3-allyl, 4-hydroxyphenylfluorene) (9,9-bis (3-allyl, 4-hydroxyphenylfluorene)) , 9,9-bis (4-allyloxyphenyl) fluorene (9,9-bis (4-allyloxyphenyl) fluorene), and 9,9-bis (3,4-methacrylic diester) fluorene (9,9-bis). It may be polymerized containing at least one selected from the group consisting of (3,4-methacryldiester) fluorene).

In the present invention, an acrylic alkali-soluble resin is used in combination with the cardo-based resin as the binder resin. That is, in the present invention, the blue photosensitive resin composition may further contain an acrylic alkali-soluble resin in the cardo-based resin.

Examples of the acrylic alkali-soluble resin include a carboxyl group-containing monomer and a copolymer of this monomer with another copolymerizable monomer. Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, and other unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. Examples include carboxylic acid. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic acid anhydride, and citraconic acid anhydride. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl), phthalic acid. Examples thereof include mono (2-acryloyloxyethyl) and mono (2-methacryloyloxyethyl) phthalate. The unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxypolymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used alone or in admixture of two or more. Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o. -Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p. -Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and inden; 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-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl Acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, 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 glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate G, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy Unsaturated carboxylic acid esters such as -3-phenoxypropyl methacrylate, glycerol monoacrylate, 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 methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl ether , Unsaturated ethers such as vinyl ethyl ether, allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylicamide, α-chloroacrylamide, N-2- Unsaturated amides such as hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylate; unsaturated imides such as maleimide, benzyl maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; 1,3-butadiene, isoprene, chloroprene and the like. Lipid-conjugated dienes; and monoacryloyl or monomethacryloyl groups at the ends of the polymer molecular chains of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. Examples thereof include giant monomers having. These monomers can be used alone or in admixture of two or more. In particular, as another monomer copolymerizable with the carboxyl group-containing monomer, a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantan skeleton, and a monomer having a rosin skeleton. This is preferable because the body tends to lower the specific dielectric constant value.

The cardo-based binder resin and / or acrylic-based alkali-soluble resin of the present invention preferably has an acid value in the range of 20 to 200 (KOHmg / g). When the acid value is within the above range, the solubility in the developing solution is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development and the residual film ratio. (Film remaining ratio) is improved, which is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is usually titrated with an aqueous potassium hydroxide solution. Desired. Further, the polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an elution solvent) is 2,000 to 200,000, preferably 3,000. 100,000 cardo-based binder resin or acrylic-based resin is preferable. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developing solution is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the cardo-based binder resin and / or the acrylic resin is preferably 1.0 to 6.0, preferably 1.5 to 6.0. The one is more preferable. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, the developability is excellent, which is preferable.

The binder resin of the present invention may be contained in an amount of 5 to 85% by weight, preferably 5 to 60% by weight, based on the total weight of solids in the blue photosensitive resin. When the content of the binder resin is used in the above range, the solubility in the developing solution is sufficient, the development residue is less likely to be generated on the substrate of the non-pixel portion, and the film of the pixel portion of the exposed portion is less likely to be reduced during development. Therefore, the non-pixel portion tends to have good omission, which is preferable.

Photopolymerizable Compound The photopolymerizable compound contained in the blue photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer or bifunctional monopolymer. Examples include polymers and other polyfunctional monomers. Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Specific 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. Examples thereof include bis (acryloyloxyethyl) ether of A and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. Examples include (meth) acrylate. Of these, polyfunctional monomers having two or more functions are preferably used. The photopolymerizable compound may be contained in an amount of 5 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of the solid content in the blue photosensitive resin. When the content of the photopolymerizable compound satisfies the above range, the strength and smoothness of the pixel portion tend to be good, which is preferable.

Photoinitiator The photopolymerization initiator used in the present invention plays a role of improving the sensitivity of the photosensitive resin composition and increasing the productivity, and the photoinitiator is represented by the following chemical formulas 1 to 3. It may be at least one selected from the compounds.

（前記化学式１において、
Ｒ_１〜Ｒ_４は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、炭素数１〜１２のアルキル基で置換もしくは非置換のフェニル基、炭素数１〜１２のアルキル基で置換もしくは非置換のベンジル基、または炭素数１〜１２のアルキル基で置換もしくは非置換のナフチル基である。）

(In the chemical formula 1,
R _{1 to} R ₄ are independently substituted or unsubstituted with a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It is a naphthyl group substituted or unsubstituted with a benzyl group or an alkyl group having 1 to 12 carbon atoms. )

（前記化学式２において、Ｒ_５は、水素、炭素数１〜２０のアルキル基、炭素数３〜８のシクロアルキル基、または置換されないか、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基で置換されたフェニル基であるか、

であり、ｎは、１〜４の整数であり、ｍは、１〜６の整数であり；
Ｒ_６は、炭素数１〜８のアルキル基、フェニル基、置換フェニル基、ベンジル基、または置換ベンジル基；
Ｒ_７は、ジフェニルスルフィド基、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基で置換されたジフェニルスルフィド基、カルバゾール基、メチル基、メトキシ基、ハロゲン、カルボキシル基、およびヒドロキシ基でカルバゾール基、フルオレン基、または置換フルオレン基である。）

(In the chemical formula 2, R ₅ is a hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an unsubstituted or methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group. Is it a phenyl group substituted with?

N is an integer of 1 to 4 and m is an integer of 1 to 6;
R ₆ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group, or a substituted benzyl group;
R ₇ is a diphenyl sulfide group substituted with a diphenyl sulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a carbazole group with a hydroxy group. , A fluorene group, or a substituted fluorene group. )

（前記化学式３において、
Ｒ_８、Ｒ_９およびＲ_１０は、それぞれ独立に、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’、またはＣＮを示し；
ＲおよびＲ’は、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基、または炭素数２〜２０の複素環基を示し、これらは、ハロゲン原子および／または炭素数２〜２０の複素環基で置換されていてもよいし、これらのうち、アルキル基およびアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合によって中断されていてもよく、また、ＲおよびＲ’は、共に環を形成してもよいし；
Ｙ_１は、酸素原子、硫黄原子、またはセレン原子を示し、ｍは、０〜４の整数を示し、ｐは、０〜５の整数を示し；
ｑは、０または１を示し；
Ｒ_１１、Ｒ_１２、Ｒ_１３およびＲ_１４は、それぞれ独立に、水素原子、ハロゲン原子、または炭素数１〜８のアルキル基を示し；
Ｘ_１は、炭素数１〜２０のアルキル基、炭素数６〜３０のアリール基、炭素数７〜３０のアラルキル基、または炭素数２〜２０の複素環基を示し、これらは、ハロゲン原子、および／または炭素数２〜２０の複素環基で置換されていてもよいし、これらのうち、アルキル基およびアラルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合によって中断されていてもよく；
Ｙ_２およびＹ_３は、それぞれ独立に、酸素原子、硫黄原子、またはセレン原子を示す。）

(In the chemical formula 3,
R ₈ , R ₉ and R ₁₀ independently represent R, OR, COR, SR, CONRR', or CN;
R and R'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogens. It may be substituted with an atomic and / or heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. R and R'may form a ring together;
Y ₁ represents an oxygen atom, a sulfur atom, or a selenium atom, m represents an integer of 0 to 4, and p represents an integer of 0 to 5;
q indicates 0 or 1;
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms;
X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms. And / or may be substituted with a heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. May be;
Y ₂ and Y ₃ independently represent an oxygen atom, a sulfur atom, or a selenium atom. )

Preferably, as the alkyl group represented by R and R', for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl. , Isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyroxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyroxyethoxy Ethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazole-2'-yl) ethenyl and the like can be mentioned, and among them, the number of carbon atoms is 1 to 8. Alkyl group is preferred.

Examples of the aryl group represented by R and R'include phenyl, trill, xsilyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like, and among them, the number of carbon atoms is 6 to 6. Twelve aryl groups are preferred. Further, as the aralkyl group represented by R and R', for example, benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like, aralkyl having 7 to 13 carbon atoms. Groups are preferred. As the heterocyclic group represented by R and R', for example, a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, and thiophenyl is preferably mentioned. Further, as a ring in which R and R'may be formed together, for example, a ring having 5 to 7 carbon atoms such as a piperidine ring and a morpholine ring is preferably mentioned. In addition, R and R'are replaced with halogen elements such as fluorine, chlorine, bromine, and iodine, or pyridyl, pyrimidyl, frill, benzoxazole-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolydyl. (Pyrazolidyl), thiazolidyl, isothiazolydyl, oxazolidyl, isooxazolidyl, piperidyl, piperidyl, heterocyclic number of piperidines, piperidines, piperidines, piperidines, piperidines, piperidines, piperidines, piperidines It may be replaced with.

Preferably, the _{alkyl group represented by X 1} includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl and isooctyl. , 2-Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, aryl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyroxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyroxyethoxyethyl, Examples thereof include methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazole-2'-yl) ethenyl, and among them, alkyl having 1 to 8 carbon atoms. Group is preferred.

Examples of the aryl group represented by X ₁ include phenyl, trill, xsilyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, and the like, and among them, the number of carbon atoms is 6 to 12. Aryl groups are preferred. Further, _{examples of the aralkyl group represented by X 1} include aralkyl groups having 7 to 13 carbon atoms such as benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and phenylethenyl. Preferred. As the _{heterocyclic group represented by X 1} , for example, a heterocyclic group having 5 to 7 carbon atoms such as pyridyl, pyrimidyl, furyl, and thiophenyl is preferably mentioned.

Examples of the halogen atom represented by X ₁ include fluorine, chlorine, bromine and iodine. The alkyl group represented by X ₁ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, which are substituted or not substituted with halogen atoms. , Octyl, isooctyl, 2-ethylhexyl, tert-octyl.

Examples of the halogen atom represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ include fluorine, chlorine, bromine and iodine.

The _{alkyl groups represented by R 11} , R ₁₂ , R ₁₃ and R ₁₄ are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl. , Isooctyl, 2-ethylhexyl, tert-octyl.

The compound represented by the chemical formula 3 may be the following compound.

The compounds represented by the chemical formula 1 are 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-methyl-2-amino (4-morpholinophenyl) ethane-1-. On, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-) Morphorinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butane-1-one, 2-ethyl -2-Amino (4-morpholinophenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butane-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propane Selected from the group consisting of -1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, and 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one. It may be more than one kind.

As a commercially available product, the compound represented by Chemical Formula 2 may be one or more selected from the group consisting of Irgacure OXE-01 (BASF) and TR-PBG-305 (Trolly).

The compound represented by Chemical Formula 3 may be N-1919 (Adeka Corporation) as a commercially available product.

The blue photosensitive resin composition of the present invention contains at least one photoinitiator selected from the compounds represented by chemical formulas 1 to 3 in the blue photosensitive resin composition to increase the development speed. It is possible to realize a color filter having excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability, particularly a self-luminous color filter.

The photopolymerization initiator used in the blue photosensitive resin composition according to the present invention is 0.1 to 30% by weight, preferably 0.3 to 20% by weight, based on the total solid content in the blue photosensitive resin. % May be included. If it is within the above range, the sensitivity of the colored photosensitive resin composition is increased, and the strength of the pixel portion formed by using this composition and the smoothness on the surface of the pixel portion tend to be improved. preferable.

Further, in the present invention, a photopolymerization initiator can be used. The photopolymerization initiator is a compound that may be used in combination with a photopolymerization initiator and is used to promote the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, Examples thereof include 4'-bis (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. .. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Such a photopolymerization initiator may be used alone or in combination of two or more without any problem. Further, a commercially available photopolymerization initiator can be used, and examples of the commercially available photopolymerization initiator include the trade name "EAB-F" [manufacturer: Hodogaya Chemical Co., Ltd.]. Be done.

When these photopolymerization initiators are used, the amount used is usually 10 mol or less, preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. Within the above range, the sensitivity of the blue photosensitive resin composition is further increased, and the productivity of the color filter formed by using this composition tends to be improved, which is preferable.

Antioxidant The antioxidant used in the present invention can effectively suppress and prevent the decrease in fluorescence efficiency by capturing radicals generated by heat during post-baking and reacting the radicals with the fluorescent dye. , The radical scavenging effect is excellent, and a sufficient effect can be expected even when used with a small content.

The antioxidant is at least one selected from phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants.

Radicals generated from the photopolymerization initiator reduce the fluorescence efficiency and may cause yellowing due to the baking step performed in the manufacturing step. At least one or more antioxidants selected from phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants are selected from compounds represented by chemical formulas 1 to 3. By combining with one or more photopolymerization initiators, at least one or more antioxidants selected from the phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants can be photopolymerized. By using an antioxidant, it is possible to suppress the occurrence of yellowing caused by the initiator and solve the problem of reduced fluorescence efficiency. In addition, it can be excellent in taperness and straightness.

The antioxidant can include one or more selected from the group consisting of phenolic compounds, phosphorus compounds, and sulfur compounds, which are phenolic-phosphorus compounds, phenolic-sulfur compounds, It can be used in a combination of a phosphorus-based-sulfur-based compound or a phenol-based-phosphorus-based compound.

The type of phenolic antioxidant is not particularly limited, but specific examples include 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1. , 1-Dimethylethoxy] -2,4,8,10-Tetraoxaspiro [5.5] Undecane, Pentaerytrityl 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, triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-4-hydroxy) Benzyl) -isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol-bis [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) 4-Hydroxybenzyl) benzene, 2,4-bis [(octylthio) methyl] -O-cresol, 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate], octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidene- Bis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) ) Benzyl, tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane and the like.

In the phenolic antioxidant, from the viewpoint of heat resistance and heat discoloration prevention, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1-Dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5,-trimethyl-2,4,6, -tris (3'5'-di- t-Butyl-4-hydroxybenzyl) benzene, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-4-hydroxy) Benzyl) -isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol-bis [3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) 4-Hydroxybenzyl) benzene and 2,4-bis [(octylthio) methyl] -O-cresol are preferred.

Examples of commercially available products include Irganox 1010 (manufactured by BASF), Sumilizer BBM-S (manufactured by Sumitomo Chemical), ADK STAB AO-80 (manufactured by ADEKA), Sumilizer GP (manufactured by Sumitomo Chemical), and Irganox 1035 (manufactured by BASF).

The type of phosphorus-based antioxidant is not particularly limited, but specific examples thereof include 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-. 3,9-Diphosphaspiro [5.5] undecane, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di) -T-Butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-) Methyl-6-t-butylphenylditridecyl) phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3) , 5-Di-t-Butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neo Pentantetraylbis (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (2,4-di-t-) Butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) ) -6-Methylphenyl] ethyl ester, phosphonic acid and the like.

Among the phosphorus-based antioxidants, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, 3 , 9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, and 6- [3-( 3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine, etc. preferable.

The type of sulfur-based antioxidant is not particularly limited, but specific examples thereof include 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- ( Dodecylthio) propionate], 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaeri Examples thereof include trityl-tetrakis (3-laurylthiopropionate) and 2-mercaptobenzimidazole.

Among the sulfur-based antioxidants, 2,2-bis ({[3 (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- ( Dodecylthio) propionate], 2-mercaptobenzimidazole and the like are preferable.

The antioxidant may be contained in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total solid content of the blue photosensitive resin composition of the present invention. When the content of the antioxidant satisfies the above range, it is advantageous in terms of solving the problem of reduced fluorescence efficiency.

Solvent The solvent contained in the blue photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of the blue photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol di. Diethylene glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxy. Alkylene glycol alkyl ether acetates such as pentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, Examples thereof include alcohols such as hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. Among the solvents, from the viewpoint of coatability and drying property, it is possible to preferably have an organic solvent having a boiling point of 100 ° C. to 200 ° C., and more preferably alkylene glycol alkyl ether acetates and ketones. , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3 -Methyl methoxypropionate and the like. These solvents can be used alone or in admixture of two or more.

The content of the solvent in the blue photosensitive resin composition of the present invention may be 50 to 90% by mass, preferably 55 to 85% by mass, based on the total amount of the blue photosensitive resin composition containing the solvent. If the content of the solvent is in the range of 50 to 90% by mass based on the above standard, it is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also called a die coater), or an inkjet. At times, the coatability tends to be good, which is preferable.

Additives The blue photosensitive resin composition according to the present invention contains, if necessary, fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like. The agent may be additionally included.

Specific examples of the filler include glass, silica, alumina and the like.

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

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. Be done. These can be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl diethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Yes, and other product names include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (POLYFLOW) (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), Megafuck (MEGAFAC). (Manufactured by Dainippon Ink and Chemicals Co., Ltd.), Florad (Manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surfron (Manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (Manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.) and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples thereof include trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The additive can be appropriately added and used by those skilled in the art as long as the effect of the present invention is not impaired. For example, the additive is 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the entire blue photosensitive resin composition. It can be used, but is not limited to this.

The blue photosensitive resin composition according to the present invention is produced, for example, by the following method. The scattered particles are mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle size becomes 10 to 1000 nm. At this time, if necessary, a dispersant may be additionally used, and a part or all of the binder resin (cardo resin or a mixture of the cardo resin and the acrylic alkali-soluble resin) is blended. May be good. In the obtained dispersion (hereinafter, also referred to as mill base), the residue of the binder resin (cardo resin or a mixture of the cardo resin and the acrylic alkali-soluble resin), a blue colorant, a photopolymerizable compound, and chemical formula 1 -At least one selected from the compounds represented by Chemical Formula 3, at least one selected from phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants, is required. Other components used accordingly and, if necessary, additional solvents can be further added to a predetermined concentration to obtain the desired blue photosensitive resin composition.

<Color filter and image display device>
Another aspect of the present invention relates to a color filter containing a blue pattern layer containing a cured product of the above-mentioned blue photosensitive resin composition for forming a blue pattern layer.

Since the color filter according to the present invention is manufactured by the above-mentioned blue photosensitive resin composition for forming a blue pattern layer instead of the blue quantum dots, there is an advantage that the manufacturing cost can be reduced. Further, by containing at least one photoinitiator selected from the compounds represented by Chemical Formulas 1 to 3 in the blue photosensitive resin composition of the present invention, the development speed is excellent and the processability is excellent. When formed into a cured film, it is possible to realize a color filter having excellent heat resistance and light resistance and excellent reliability, particularly a self-luminous color filter. Further, if necessary, the blue photosensitive resin composition of the present invention may further contain at least one selected from a phosphorus-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant. , Excellent processability and reliability can be ensured.

The color filter includes a substrate and a blue pattern layer formed on the upper part of the substrate.

The substrate may be the color filter itself substrate, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC). And so on.

The blue pattern layer is a layer containing the blue photosensitive resin composition of the present invention, and is formed by applying the blue photosensitive resin composition for forming the blue pattern layer and exposing, developing, and thermosetting the predetermined pattern. The pattern layer may be formed by a method generally known in the art.

In yet another embodiment of the invention, the color filter may further include one or more selected from the group consisting of a red pattern layer and a green pattern layer.

In yet another embodiment of the invention, the red or green pattern layer can include quantum dots and / or scattered particles. Specifically, the color filter according to the present invention can include a red pattern layer containing red quantum dots or a green pattern layer containing green quantum dots, and the red pattern layer or green pattern layer contains scattered particles. be able to. The red pattern layer or the green pattern layer can emit red light or blue light, respectively, by a light source that emits blue light, which will be described later.

In still another embodiment of the present invention, the scattered particles contained in the red pattern layer or the green pattern layer can contain a metal oxide having an average particle size of 10 to 1000 nm, and the scattered particles and the metal oxide are related to the scattered particles and the metal oxide. As the content, the content relating to scattered particles and metal oxides contained in the blue photosensitive resin composition according to the present invention can be applied.

In the present invention, the form, composition, and content of the quantum dots contained in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art can be applied.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix, but is not limited thereto.

In the present invention, the color filter may be a self-luminous color filter.

Yet another aspect of the present invention relates to an image display device including the color filter described above and a light source that emits blue light. In short, the image display device according to the present invention includes a color filter including a blue pattern layer containing a cured product of the blue photosensitive resin composition described above, and a light source that emits blue light.

The color filter of the present invention can be applied not only to a normal liquid crystal display device but also to various image display devices such as a field emission display device, a plasma display device, and a field emission display device.

When the image display device includes the color filter including the blue pattern layer according to the present invention and the light source, there is an advantage that the image display device has excellent emission intensity. Further, since the blue pattern layer included in the color filter according to the present invention does not contain blue quantum dots, there is an advantage that an image display device having a low manufacturing cost can be manufactured.

Hereinafter, in order to specifically explain the present specification, examples will be given and described in detail. However, the embodiments according to the present specification can be transformed into various different forms, and the scope of the present specification is not construed as being limited to the examples detailed below. The examples herein are provided to provide a more complete description of the specification to those with average knowledge in the art. In addition, hereinafter, “%” and “part” indicating the content are based on weight unless otherwise specified.

Synthesis example: Synthesis of binder resin Production example 1: Acrylic-based alkali-soluble resin A flask equipped with a stirrer, a thermometer reflux-cooling tube, a dropping funnel and a nitrogen introduction tube is prepared, while benzylmaleimide 74. 8 g (0.20 mol), 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyl toluene, 4 g of t-butylperoxy-2-ethylhexanoate, propylene glycol monomethyl ether After adding 40 g of acetate (PGMEA), the mixture was prepared by stirring and mixing, and as a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and mixed by stirring. After that, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were started to be added dropwise from the dropping funnel. The dropping was carried out for 2 hours while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 hours, and then a gas introduction pipe was introduced to oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis (4-methyl-6-t). -Butylphenol) 0.4 g and triethylamine 0.8 g were put into a flask, and the reaction was continued at 110 ° C. for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH / g. The polystyrene-equivalent weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Production Example 2: Synthesis of Compound of Chemical Formula 6 In a 3000 ml 3-neck round bottom flask, 3', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6'-dihydroxyspiro (fluorene-9,9)) -Xanthene)) 364.4 g and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely exhausted by analysis by liquid chromatography, the mixture was cooled to 30 ° C. and a 50% aqueous NaOH solution (3 equivalents) was slowly added. After analysis by liquid chromatography and complete exhaustion of epichlorohydrin, extraction with dichloromethane, washing with water three times, drying the organic layer with magnesium sulfate, distillation of dichloromethane under reduced pressure, dichloromethane and methanol It was recrystallized using a mixing ratio of 50:50 with.

After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, the solvent propylene glycol monomethyl ether acetate 24 .89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH / g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Chemical Formula 6.

Production Example 3: Synthesis of Compound of Chemical Formula 7 In a 3000 ml 3-neck round bottom flask, 3', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6'-dihydroxyspiro (fluorene-9,9)) -Xanthene)) 364.4 g and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely exhausted by analysis by liquid chromatography, the mixture was cooled to 30 ° C. and a 50% aqueous NaOH solution (3 equivalents) was slowly added. When epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50.

After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid, the solvent propylene glycol monomethyl ether acetate is used. 24.89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH / g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Chemical Formula 7.

Production Example 4: Synthesis of Compound of Chemical Formula 8 In a 3000 ml 3-neck round bottom flask, 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9H-xanthene-9,, 364.4 g of 9-diyl) diphenyl) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When analyzed by liquid chromatography and the 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenyl) is completely exhausted, the temperature is 30 ° C. And a 50% aqueous NaOH solution (3 eq) was added slowly. When epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50. After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, the solvent propylene glycol monomethyl ether acetate 24 .89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH / g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Chemical Formula 8.

Production Example 5: Synthesis of Compound of Chemical Formula 9 In a 3000 ml 3-neck round bottom flask, 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9H-xanthene-9,, 364.4 g of 9-diyl) diphenyl) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was heated to 90 ° C. for reaction. When analyzed by liquid chromatography and the 4,4'-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenyl) is completely exhausted, the temperature is 30 ° C. And a 50% aqueous NaOH solution (3 eq) was added slowly. When epichlorohydrin is completely exhausted by analysis by liquid chromatography, it is extracted with dichloromethane, washed with water three times, the organic layer is dried with magnesium sulfate, and dichloromethane is distilled under reduced pressure. It was recrystallized using a mixing ratio of 50:50. After mixing 1 equivalent of the epoxy compound thus synthesized, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid, the solvent propylene glycol monomethyl ether acetate is used. 24.89 g was added and mixed. The reaction solution was heated and dissolved at a temperature of 90 to 100 ° C. while blowing air at 25 ml / min. The reaction solution was heated to 120 ° C. in a cloudy state to completely dissolve it. When the solution became transparent and the viscosity became high, the acid value was measured and stirred until the acid value became less than 1.0 mgKOH / g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound of Chemical Formula 9.

Production Example 6: Synthesis of cardo-based binder resin (A-1)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 6 of Production Example 2 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated. The reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3500

Production Example 7: Synthesis of cardo-based binder resin (A-2)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 7 of Production Example 3 and dissolving it, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated. The reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 3800

Production Example 8: Synthesis of cardo-based binder resin (A-3)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 8 of Production Example 4 and dissolving it, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated. The reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4500

Production Example 9: Synthesis of cardo-based binder resin (A-4)
After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Chemical Formula 9 of Production Example 5 and dissolving it, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated. The reaction was carried out at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize on a cardo-based binder resin. The disappearance of the anhydride was confirmed by IR spectrum. Weight average molecular weight: 4900
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40 ° C
Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by weight (solvent = tetrahydrofuran)
Calibration standard material: TSK STANDARD polystyrene F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and the number average molecular weight obtained above was defined as the molecular weight distribution (Mw / Mn).

Examples 1 to 25 and Comparative Examples 1 to 6: Production of Blue Photosensitive Resin Composition The blue photosensitive resin compositions of Examples 1 to 25 and Comparative Examples 1 to 6 are produced according to the compositions shown in Tables 1 to 3 below. did.

1) Blue colorant:
B-1: Fastogen Blue EP-7S (DCI): C.I. I. Pigment Blue 15: 6
B-2: Fastogen Blue5424 (DCI): C.I. I. Pigment Blue 15: 4
V-1: Fastogen Super Violet 140V (DIC Corporation): C.I. I. Pigment Violet 23
2) Scattered particles (E-1): TioxideR TR88 (Huntsman)
3) Binder resin:
A-1: Cardo-based resin of Production Example 6,
A-2: Cardo-based resin of Production Example 7,
Acrylic resin: Acrylic alkali-soluble resin of Production Example 1 4) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
5) Photoinitiator C-1: Compound of Chemical Formula 1: IRGACURER369 (BASF)
C-2: Compound of Chemical Formula 2: TR-PBG-305 (Trolly)
C-3: Compound of Chemical Formula 3: N-1919 (Adeka Corporation)
C-4: IRGACURER907 (manufactured by BASF)
6) Antioxidant Antioxidant A: 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant Antioxidant B: Bis [3] -(Dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name: Sumilyzer TP-D: sulfur-based oxidation Antioxidant Antioxidant C: IrgafosR126 (BASF): Phosphoric antioxidant 7) Solvent: Propyl glycol monomethyl ether acetate

1) Blue colorant:
B-1: Fastogen Blue EP-7S (DCI): C.I. I. Pigment Blue 15: 6
B-2: Fastogen Blue5424 (DCI): C.I. I. Pigment Blue 15: 4
V-1: Fastogen Super Violet 140V (DIC Corporation): C.I. I. Pigment Violet 23
2) Scattered particles (E-1): TioxideR TR88 (Huntsman)
3) Binder resin:
A-1: Cardo-based resin of Production Example 6,
A-2: Cardo-based resin of Production Example 7,
Acrylic resin: Acrylic alkali-soluble resin of Production Example 1 4) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
5) Photoinitiator C-1: Compound of Chemical Formula 1: IRGACURER369 (BASF)
C-2: Compound of Chemical Formula 2: TR-PBG-305 (Trolly)
C-3: Compound of Chemical Formula 3: N-1919 (Adeka Corporation)
C-4: IRGACURER907 (manufactured by BASF)
6) Antioxidant Antioxidant A: 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant Antioxidant B: Bis [3] -(Dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name: Sumilyzer TP-D: sulfur-based oxidation Antioxidant Antioxidant C: IrgafosR126 (BASF): Phosphoric antioxidant 7) Solvent: Propyl glycol monomethyl ether acetate

1) Blue colorant:
B-1: Fastogen Blue EP-7S (DCI): C.I. I. Pigment Blue 15: 6
B-2: Fastogen Blue5424 (DCI): C.I. I. Pigment Blue 15: 4
V-1: Fastogen Super Violet 140V (DIC Corporation): C.I. I. Pigment Violet 23
2) Scattered particles (E-1): TioxideR TR88 (Huntsman)
3) Binder resin:
A-1: Cardo-based resin of Production Example 6,
A-2: Cardo-based resin of Production Example 7,
Acrylic resin: Acrylic alkali-soluble resin of Production Example 1 4) Photopolymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
5) Photoinitiator C-1: Compound of Chemical Formula 1: IRGACURER369 (BASF)
C-2: Compound of Chemical Formula 2: TR-PBG-305 (Trolly)
C-3: Compound of Chemical Formula 3: N-1919 (Adeka Corporation)
C-4: IRGACURER907 (manufactured by BASF)
6) Antioxidant Antioxidant A: 4,4'-butylidenebis (6-tert-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S): Phenolic antioxidant Antioxidant B: Bis [3] -(Dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl (Sumitomo Chemical, trade name: Sumilyzer TP-D: sulfur-based oxidation Antioxidant Antioxidant C: IrgafosR126 (BASF): Phosphoric antioxidant 7) Solvent: Propyl glycol monomethyl ether acetate

Production of Color Filter A color filter was produced using the blue photosensitive resin compositions produced in Examples 1 to 25 and Comparative Examples 1 to 6. That is, each of the blue photosensitive resin compositions was applied onto a glass substrate by a spin coating method, then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Next, a test photomask having a horizontal × vertical (20 mm × 20 mm) regular quadrangular transmission pattern and a line / space pattern of 1 to 100 μm is placed on the thin film, and the distance from the test photomask is set to 100 μm. Irradiated with ultraviolet rays.

At this time, the ultraviolet light source is an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio, Inc., which is irradiated with light at an exposure amount (365 nm) of ^{200 mJ / cm 2 in an atmospheric atmosphere, and special optics is used.} No filter was used.

The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development. The glass plate covered with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to produce a color filter pattern. The film thickness of the color pattern produced above was 5.0 μm.

Test Example 1: Heat resistance evaluation For heat resistance, the chromaticity and transmittance of the substrate manufactured by manufacturing the color filter are measured with a chromaticity meter (OSP-200 manufactured by Olympus), and the measurement of color coordinates is completed. After heating the substrate at 230 ° C. for 120 minutes, the chromaticity and transmittance were remeasured with a chromaticity meter (OSP-200 manufactured by Olympus). The heat resistance was evaluated by measuring the color change value (ΔEab) after heating at 230 ° C. for 120 minutes. ΔEab is a value obtained by the following saturation formula based on the CIE1976 (L *, a *, b *) spatial color system (New Color Science Handbook edited by the Japan Color Society (1985) p.266).
△ Eab * = [(△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² ] ^1/2

[Heat resistance evaluation criteria]
◯: ΔEab * value: 3 or less Δ: ΔEab * value: 3 excess to 10 or less X: ΔEab * value: 10 excess

Test Example 2: Evaluation of light resistance For light resistance, the chromaticity and transmittance of the substrate manufactured by manufacturing the color filter are measured with a chromaticity meter (OSP-200 manufactured by Olympus), and the measurement of color coordinates is completed. After irradiating the light-resistant equipment (ATLAS CPS + equipment) for 200 hours, the chromaticity and transmittance were remeasured with a chromaticity meter (OSP-200 manufactured by Olympus).
ΔEab is a value obtained by the following saturation formula based on the CIE1976 (L *, a *, b *) spatial color system (New Color Science Handbook edited by the Japan Color Society (1985) p.266).
△ Eab ^* = [(△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² ] ^1/2

[Light resistance evaluation criteria]
◯: ΔEab * value: 3 or less Δ: ΔEab * value: 3 excess to 10 or less X: ΔEab * value: 10 excess

Experimental Example 3: Development speed After applying each of the blue photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 on a glass substrate by a spin coating method, they are placed on a heating plate and placed at a temperature of 100 ° C. for 3 After maintaining for a minute to form a thin film, after ^{irradiating with ultraviolet rays of 50 mJ / cm 2} with full exposure without a photomask, the film thickness of the pattern was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). It was measured. The substrate for which the thickness measurement was completed was further immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds for development, and then the presence or absence of the blue photosensitive resin composition remaining in the unexposed portion was confirmed.

[Development speed evaluation criteria]
During development, the time required for the unexposed area to completely dissolve in the developing solution was measured and shown in seconds. When it was not developed, it was indicated as "x".

The evaluation results of heat resistance, light resistance and development speed are shown in Table 4 below.

Experimental Example 4: Evaluation of pattern taperness and straightness The taper and pattern straightness of a color filter produced with the blue photosensitive composition obtained in Examples 8 to 25 and Comparative Examples 3 to 6 were applied. The properties were observed by observing the shape of the pixel surface with SEM (10,000 magnification), and the results are shown in Table 4 below. At this time, the taper property and the pattern straightness are as follows.

<Taperity>
◯: Good pattern profile (Pattern profile) X: Poor pattern profile (Pattern profile)

<Straightness>
◯: Straightness deviation of the pattern edge (Pattern edge) portion is 1 μm or less X: Straightness deviation of the pattern edge (Pattern edge) portion exceeds 1 μm.

Test Example 5: Measurement of Emission Intensity Of the color filters produced using the blue photosensitive resin compositions produced in Examples 8 to 25 and Comparative Examples 3 to 6, they were formed into a square pattern of 20 × 20 mm. The region light-converted by a 365 nm Tube type 4W UV irradiator (VL-4LC, VILBER LOURMAT) was measured in the portion, and Examples 8 to 25 and Comparative Examples 3 to 6 showed the emission intensity in the region of 450 nm. Was measured using a Spectram meter (Ocean Optics). The measurement results are shown in Table 4.

As can be seen from the results in Table 4, in the case of the example containing at least one photoinitiator selected from the compounds represented by Chemical Formulas 1 to 3, excellent heat resistance and light resistance. It can be seen from Examples 1 to 7 that the development speed is also excellent. Further, in the cases of Examples 8 to 25 in which the antioxidant A, the antioxidant B, or the antioxidant C is selectively further contained as the antioxidant, the taper property, the straightness, and the light emission intensity are excellent. You can see that.

On the other hand, in the cases of Comparative Examples 1 and 2, the developing speed was slower than that of Examples, and the results were not excellent in heat resistance and light resistance. Further, in the cases of Comparative Examples 3 to 6, it is confirmed that the processability is lowered due to the deterioration of heat resistance, light resistance, taperness, and straightness, and it can be confirmed that the light emission intensity is not excellent.

The blue photosensitive resin composition of the present invention contains at least one photoinitiator selected from the compounds represented by chemical formulas 1 to 3 in the blue photosensitive resin composition to increase the development speed. It is possible to realize a color filter having excellent processability, excellent heat resistance and light resistance when formed into a cured film, and excellent reliability, particularly a self-luminous color filter.

Claims (15)

It contains scattered particles, a blue colorant, a cardo-based binder resin as a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.
The photoinitiator is at least one selected from the compounds represented by the following chemical formulas 1 to 3.
The blue photosensitive resin composition, wherein the cardo-based binder resin contains one or more of the compounds represented by the following chemical formulas 4-1 and 4-2.

(In the chemical formula 1,
R _{1 to} R ₄ are independently substituted or unsubstituted with a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It is a naphthyl group substituted or unsubstituted with a benzyl group or an alkyl group having 1 to 12 carbon atoms. )

(In the chemical formula 2,
Is R ₅ a hydrogen, an alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 8 carbon atoms, or a phenyl that is not substituted or is substituted with a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group? ,

N is an integer of 1 to 4 and m is an integer of 1 to 6;
R ₆ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a substituted phenyl group, a benzyl group, or a substituted benzyl group;
R ₇ is substituted with a diphenyl sulfide group, a carbazole group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group substituted with a diphenyl sulfide group, a methyl group, a methoxy group, a halogen, a carboxyl group, and a hydroxy group. It is a carbazole group, a fluorene group, or a substituted fluorene group. )

(In the chemical formula 3,
R ₈ , R ₉ and R ₁₀ independently represent R, OR, COR, SR, CONRR', or CN;
R and R'represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogens. It may be substituted with an atom and / or a heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is formed by an unsaturated bond, an ether bond, a thioether bond or an ester bond. It may be interrupted, and R and R'may form a ring together;
Y ₁ represents an oxygen atom, a sulfur atom, or a selenium atom, m represents an integer of 0 to 4, and p represents an integer of 0 to 5;
q indicates 0 or 1;
R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms;
X ₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, which are halogen atoms. And / or may be substituted with a heterocyclic group having 2 to 20 carbon atoms, of which the alkylene moiety of the alkyl group and the aralkyl group is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. May be;
Y ₂ and Y ₃ independently represent an oxygen atom, a sulfur atom, or a selenium atom.
)

(In the chemical formulas 4-1 and 4-2,
R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are independent of each other.

Is;
X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, and R ₁₉ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ). Contains more oxidants,
The blue photosensitive agent according to claim 1, wherein the antioxidant is at least one selected from a phosphorus-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant. Sex resin composition. The phosphorus-based antioxidant is 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5]. Undecane, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-Ethylhexyloxy) phosphorus, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] Dioxaphosfepine, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) ) Phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4) -Hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di) -T-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2, 4-Di-t-Butylphenyl) [1,1-biphenyl] -4,4'diylbisphosphonite, and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester , One or more selected from the group consisting of phosphonic acid;
The sulfur-based antioxidants are 2,2-bis ({[3- (dodecylthio) propionyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate], 2-mercaptobenzimidazole. , Dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiopropio) Nate), and one or more selected from the group consisting of 2-mercaptobenzimidazole;
The phenolic antioxidant is 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethoxy] -2,4. , 8,10-Tetraoxaspiro [5.5] undecane, pentaerythrityl 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, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy) Phenyl) propionate], 4,4'-thiobis (6-t-butyl-3-methylphenol), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3 5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxy) Phenol) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,4 -Bis [(octylthio) methyl] -O-cresol, 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl 3- (3, 5-Di-tert-butyl-4-hydroxyphenol) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-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- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] The blue photosensitive resin composition according to claim 2, which is one or more selected from the group consisting of methane. The compounds represented by the chemical formula 1 are 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-methyl-2-amino (4-morpholinophenyl) ethane-1. -On, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4) -Molholinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butane-1-one, 2- Ethyl-2-amino (4-morpholinophenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butane-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) Selected from the group consisting of propane-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, and 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition is at least one kind. The blue photosensitive resin composition according to claim 1, wherein the scattered particles contain a metal oxide having an average particle size of 10 to 1000 nm. The scattered particles are a _{group consisting of Al 2} O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTIO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO-Al, Nb ₂ O ₃ , SnO, and MgO. The contained blue photosensitive resin composition according to claim 1, which comprises one or more selected from the above. The blue photosensitive resin composition according to claim 1, wherein the scattered particle-containing blue photosensitive resin composition further contains a purple colorant. The blue photosensitive resin composition according to claim 1, wherein the blue colorant contains one or more of a blue pigment and a blue dye. The compound represented by the chemical formula 4-1 is at least one of the compounds represented by the chemical formula 6 or the chemical formula 7, and the compound represented by the chemical formula 4-2 is represented by the chemical formula 8 or the chemical formula 9. The blue photosensitive resin composition according to claim 1, which is one or more of the compounds to be used:

The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further contains an acrylic alkali-soluble resin as a binder resin. A color filter including a blue pattern layer made of the blue photosensitive resin composition according to any one of claims 1 to 10. The color filter according to claim 11, wherein the color filter further includes one or more selected from the group consisting of a red pattern layer and a green pattern layer. The color filter according to claim 12, wherein the red pattern layer or the green pattern layer includes quantum dots. The color filter according to claim 11, wherein the color filter is a self-luminous color filter. The color filter according to claim 11 and
An image display device including a light source that emits blue light.