WO2018182133A1 - Blue photo-sensitive resin composition, color filter manufactured by using same, and image display device - Google Patents

Abstract

The present invention relates to: a blue photo-sensitive resin composition containing scattered particles, a thiol compound represented by chemical formula 1, a blue colorant, a cardo-based binder resin as a binder resin, a photo-polymerizable compound, a photo-initiator, and a solvent; and a color filter comprising the same; and an image display device.

Description

 Blue photosensitive resin composition, color filter and image display device manufactured using the same

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

 The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units. The size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment-dispersible photosensitive resin has been applied, but a part of the light is absorbed by the color filter while the light emitted from the light source passes through the color filter. The problem is that the 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 this problem, a color filter manufacturing method using a self-luminous photosensitive resin composition including a quantum dot has been proposed.

Specifically, Korean Patent Publication No. 2007-0094679 suggests that color reproducibility can be improved by having a color filter layer formed of quantum dots, and Korean Patent Publication No. 2009-0036373 uses a conventional color filter as a quantum dot phosphor. It is proposed that the display quality can be improved by improving the luminous efficiency by replacing the light emitting layer.

However, until now, the photosensitive resin composition developed to manufacture a color filter did not sufficiently satisfy the requirements of excellent solvent resistance, adhesiveness, and pattern formability (fine pattern formability) when formed into a cured film. .

The present invention provides a color filter having excellent solvent resistance, adhesion and pattern formability (fine pattern formability), in particular, a blue photosensitive resin composition capable of realizing a self-luminous color filter when formed into a cured film, and a color filter manufactured using the same. It is an object to provide an image display device.

The present invention is a blue photosensitive resin composition comprising a scattering particle, a thiol compound represented by the following formula (1), a blue colorant, a binder resin, a cardo-based binder resin, a photopolymerizable compound, a photoinitiator, and a solvent,

[Formula 1]

(Formula 1, Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n Is an integer of 3 to 10, X is a C2-C70 n-valent hydrocarbon group which may have one or a plurality of ether bonds, or n is 3 and X is a trivalent group represented by the following formula (2):

[Formula 2]

(Wherein, Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond).

In addition, the present invention provides a color filter comprising a blue pattern layer made of the above-described blue photosensitive resin composition.

In addition, the present invention is the color filter; And a light source emitting blue light.

The blue photosensitive resin composition of the present invention comprises a thiol compound represented by the formula (1) in the blue photosensitive resin composition, so that the blue photosensitive resin composition has excellent solvent resistance, adhesiveness and pattern forming property when formed into a cured film. It is possible to implement a color filter having excellent fine pattern formability, particularly a self-luminous color filter.

The blue photosensitive resin composition of the present invention may include scattering particles, a thiol compound represented by Formula 1, a blue colorant, a binder resin, a cardo-based binder resin, a photopolymerizable compound, a photoinitiator, and a solvent, and in particular, a thiol represented by Formula 1 By including the compound, the blue photosensitive resin composition may be a color filter having excellent solvent resistance, adhesiveness, and pattern formability (fine pattern formability), particularly self-luminous color filter, when formed into a cured film.

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

Scattering particles

The scattering particles of the present invention may be a metal oxide having an average particle diameter of 10 to 1000 nm, more preferably when the average particle diameter is in the range of 30 to 300 nm. If the average particle diameter of the scattering particles satisfies the above range, a sufficient scattering effect of the light emitted from the quantum dots can be expected, and the scattering particles may sink in the blue photosensitive composition, or a problem may occur in which the surface of the light emitting layer may be uneven. Lowers. The metal oxide is 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, Nb, It may be an oxide including one metal selected from the group consisting of 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 , SnO, MgO and At least one selected from the group consisting of a combination thereof. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

The scattering particles may be appropriately adjusted as necessary to the average particle diameter and the content in the entire composition to sufficiently improve the light emission intensity of the color filter.

The scattering particles may be appropriately adjusted as necessary to the average particle diameter and the content in the entire composition to sufficiently improve the light emission intensity of the color filter.

The scattering particles may be included in 0.1 to 50% by weight relative to the total weight of solids in the blue photosensitive resin, preferably 5 to 30% by weight. When the content of the scattering particles satisfies the above range, while achieving the desired emission intensity, it is possible to lower the possibility of a problem of deterioration in stability of the blue photosensitive resin composition.

Thiol compound represented by formula (1)

The thiol compound represented by the formula (1) included in the present invention serves to improve the pattern characteristics formed of the blue photosensitive resin composition and to enhance durability and reliability.

[Formula 1]

(Formula 1, Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n Is an integer of 3 to 10, X is a C2-C70 n-valent hydrocarbon group which may have one or a plurality of ether bonds, or n is 3 and X is a trivalent group represented by the following formula (2):

[Formula 2]

(In Formula 2, Z ₂ , Z ₃ and Z ₄ are independently of each other a methylene group or an alkylene group having 2 to 6 carbon atoms, "*" represents a bond).

n is preferably 4 or more, or an integer of 4 to 10, and more preferably 4, 6 or 8.

As X when n is 3, the trivalent group represented by following General formula (5) is mentioned, for example,

As X when n is 4, 6, or 8, the 4, 6, or octavalent group represented by following formula (6) etc. are mentioned as a preferable thing, respectively.

[Formula 3]

(In formula 3, "*" represents a bond.),

[Formula 4]

(In formula 4, m is an integer of 0 to 2, and "*" represents a bond.).

The thiol compound represented by Chemical Formula 1 may include at least one selected from the group consisting of compounds represented by Chemical Formulas 5 to 12, and preferably, a compound represented by Chemical Formula 5, a compound represented by Chemical Formula 9 It may include.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

By including the thiol compound represented by the formula (1) in the blue photosensitive resin composition of the present invention, the blue photosensitive resin composition is a color filter excellent in excellent solvent resistance, adhesion and pattern formability (fine pattern formability), particularly when formed into a cured film For example, the self-luminous color filter may be implemented.

The thiol compound represented by Chemical Formula 1 may be used alone or in combination of two or more thereof.

The thiol compound may be included in 0.05 to 5% by weight, preferably 0.08 to 3% by weight based on the total weight of solids in the blue photosensitive resin.

When the content of the thiol compound satisfies the above range, it is advantageous in terms of stability, smell, sensitivity, resolution, developability, and adhesion of the blue photosensitive resin composition.

Blue colorant

In the blue colorant of the present invention, examples of the blue pigment include compounds classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) as follows. Although pigment of number is mentioned, It is not necessarily limited to these. Blue pigments are specifically described, for example, in C.I. Pigment blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and the like. Pigment Blue 15: 3, Pigment Blue 15: 6, Pigment Blue 16 It is preferable to include at least 1 type selected from the group which consists of.

The blue colorant of the present invention may further comprise a blue dye, which is a known dye which is described in a compound or dyeing note (color dyed yarn) classified as a dye in the color index (published by The Society of Dyers and Colourists). And dyes.

Specific examples of the dye which can be used further include

C.I. As solvent dyes,

C.I. Solvent blue 5, 35, 36, 37, 44, 45, 59, 67 and 70, and the like. More preferably at least one of Solvent Blue 35, 36, 44, 45 and 70.

In addition, C.I. As an acid dye,

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335 and 340, among others CI More preferably, it contains one or more of acid blue 80 and 90.

In addition, C.I. As a direct dye,

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

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc. are mentioned.

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

The blue colorant of the present invention may further include a purple colorant as an additional colorant. The purple coloring agent may comprise at least one of a purple pigment and a purple dye, wherein the purple pigment is specifically C.I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among which C.I. It is more preferred to include pigment violet 23.

Purple dyes are specifically, C.I. Solvent violet, C.I. acid violet, C.I. acid violet, C.I. modanto violet, and the like, but are not limited thereto.

Specifically, the C.I. Solvent violet is C.I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49, and the like. More preferably, solvent violet 13 is included. C.I. acid violet includes C.I. Acid violet 6B, 7, 9, 17, 19 and 66, and the like. More preferably, acid violet 66 is included. CI direct violet includes CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104. .

Furthermore, CI modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc. are mentioned. .

The blue colorant may include 0.1 to 50% by weight, and preferably 0.5 to 30% by weight, based on the total weight of solids in the blue photosensitive resin. It may be included in 0.1 to 50% by weight based on 100% by weight of the blue photosensitive resin composition, 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 the external light reflection and is advantageous because it is less likely to cause a problem of lowering the luminescence intensity or a problem of lowering the viscosity stability of the blue photosensitive resin composition.

In the present invention, the blue colorant and the scattering particles are included even though the blue quantum dots are not included, thereby reducing the efficiency of the blue pixel of the color filter, particularly the self-luminous color filter.

Binder resin

The binder resin of this invention contains cardo system binder resin. The cardo-based binder resin has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The cardo-based binder resin contained in the blue photosensitive resin composition of the present invention is not limited as long as it is a resin that acts as a binder resin for scattering particles and is soluble in an alkaline developer used in the developing step for producing a color filter.

The cardo-based binder resin of the present invention may include one or more of the compounds represented by Chemical Formulas 13-1 and 13-2.

[Formula 13-1]

[Formula 13-2]

In Formulas 13-1 and 13-2,

R ₁ , R ₂ , R ₃ and R ₄ are each independently,

Is;

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

In the present invention, the compound represented by Chemical Formula 13-1 may be synthesized by the compound represented by Chemical Formula 14-1, and the compound represented by Chemical Formula 13-2 may be synthesized using the compound represented by Chemical Formula 14-2. .

[Formula 14-1]

[Formula 14-2]

The compound represented by Formula 13-1 may be any one or more of compounds represented by Formula 15 or Formula 16, and the compound represented by Formula 13-2 may be any one or more of compounds represented by Formula 17 or Formula 18.

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

The cardo-based binder resin is 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3- cinnamoyl, 4-hydride Hydroxyphenyl) fluorene (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycidyl methacrylate ether) fluorene), 9,9-bis (3,4-dihydroxyphenyl) fluorene dinamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl meta Acrylate ether spiro (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-allyl, 4-hydroxyphenylflu Orene) (9,9-bis (3-allyl, 4-hydroxyphenlylfluorene), 9,9-bis (4-allyloxyphenyl) fluorene (`9,9-bis (4-allyloxyphenyl) fluorene) and 9,9 Acid anhydrides with at least one member selected from the group consisting of bis (3,4-methacrylic diester) fluorene (9,9-bis (3,4-methacrylic diester) fluorine) Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylene anhydrous methylenetetrahydrophthalic anhydride, anhydrous chlororenic acid, methyltetrahydrophthalic anhydride, or an acid dianhydride. It can be prepared by reacting with at least one selected from the group consisting of aromatic polyhydric carboxylic acid anhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and bitenyl ether tetracarboxylic acid dianhydride. It is not limited.

The present invention is a binder resin, acrylic alkali-soluble resin may be used together with the cardo resin. That is, in the present invention, the blue photosensitive resin composition may further include an acrylic alkali-soluble resin in the cardo-based resin.

Examples of the acrylic alkali-soluble resin include carboxyl group-containing monomers and copolymers with other monomers copolymerizable with this monomer. As a carboxyl group-containing monomer, unsaturated carboxylic acids, such as unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, are mentioned, for example. have. Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy propyl 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 meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) Acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. And macromonomers to have. These monomers can be used individually or in mixture of 2 or more types, respectively. In particular, bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton as the other monomers copolymerizable with the carboxyl group-containing monomer are preferable because they tend to lower the dielectric constant. .

As the cardo binder resin and / or the acrylic alkali-soluble resin of the present invention, the acid value is preferably in the range of 20 to 200 (KOH mg / g). If the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development to improve the film remaining ratio. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution. Also, the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) is 2,000 to 200,000, preferably 3,000 to 100,000. Cardo-based binder resins and / or acrylic alkali-soluble resins are preferred. 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 developer 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 alkali-soluble resin is preferably 1.0 to 6.0, more preferably 1.5 to 6.0. If molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.

The binder resin of the present invention may be included in 5 to 85% by weight, preferably 5 to 60% by weight relative to the total weight of solids in the blue photosensitive resin. When content of binder resin is used in said range

It is preferable because the solubility in a developing solution is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and the film reduction of the pixel portion of the exposed portion is less likely to occur at the time of development, and the omission of the non-pixel portion is good.

Photopolymerizable compound

The photopolymerizable compound contained in the blue photosensitive resin composition of this invention is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc. 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, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound may be included in 5 to 50% by weight, preferably 5 to 30% by weight based on the total weight of solids in the blue photosensitive resin. When the content of the photopolymerizable compound satisfies the above range, the intensity and smoothness of the pixel portion tend to be good, which is preferable.

Photoinitiator

The photopolymerization initiator used in the present invention serves to improve the sensitivity of the photosensitive resin composition to increase productivity, and preferably contains an acetophenone-based compound. As an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1- And the like, and preferably 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) butan-1-one etc. are mentioned. Moreover, photoinitiators other than the said acetophenone series can be used in combination. Photopolymerization initiators other than the acetophenone series include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light. As an active radical generating agent, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, etc. are mentioned, for example. As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether, etc. are mentioned, for example. As a benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned. As a triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4dimethoxyphenyl) ethenyl] -1,3,5 -Triazine and the like. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-acetoxyphenyldimethylsulfonium p-toluenesulfo. Acetate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned. In addition, there are some compounds which generate an acid simultaneously with the active radicals in the compound as an active radical generator, for example, a triazine photopolymerization initiator is also used as an acid generator.

The photopolymerization initiator used in the blue photosensitive resin composition according to the present invention may be included in an amount of 0.1 to 30% by weight, preferably 0.3 to 20% by weight, based on the total weight of solids in the blue photosensitive resin. When it exists in the said range, since the coloring photosensitive resin composition becomes highly sensitive and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable.

Furthermore, in this invention, photoinitiator start adjuvant can be used. A photoinitiator adjuvant may be used in combination with a photoinitiator, and is a compound used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by a photoinitiator. As photopolymerization start adjuvant, an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.

 Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoic acid. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (commonly known as Michler's ketone), 4,4'-bis (diethyl Amino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. As an alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example. Etc. can be mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned. These photoinitiators (D) may be used alone or in combination of a plurality thereof. In addition, a commercially available thing can be used as a photoinitiator starter, As a commercially available photoinitiator starter, brand name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example.

 In the case of using these photopolymerization initiation assistants, the amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. If it exists in the said range, since the sensitivity of a coloring photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

solvent

The solvent contained in the blue photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of a 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, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl Ketones such as methyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, alcohols such as ethylene glycol, glycerin, ethyl 3-ethoxypropionate, Ester, such as 3-methoxy methyl propionate, Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned. Among the solvents described above, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy are more preferable. Ester, such as ethyl propionate and the methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent in the blue photosensitive resin composition of this invention can be contained 50-90 mass%, Preferably it is 55-85 mass% based on 100 weight% of blue photosensitive resin compositions. Applicability when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, if the content of the solvent is in the range of 50 to 90 mass% based on the above criteria. This is preferable because it tends to be good.

additive

The blue photosensitive resin composition which concerns on this invention is a filler, another high molecular compound, a pigment dispersant as needed. Additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, can be further included.

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

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively.

As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl peer ether, polyethyleneglycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

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-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The additives can be used by those skilled in the art as appropriate without departing from the effect of the present invention. For example, the additive may be used in an amount of 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 total blue photosensitive resin composition, but is not limited thereto.

The blue photosensitive resin composition which concerns on this invention can be manufactured, for example by the following method. The scattering particles are mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter becomes 10 to 1000 nm. At this time, a dispersing agent can be further used as needed, and some or all of binder resin (cardo resin or mixture of cardo resin and acrylic alkali-soluble resin) may be mix | blended. Thiol compound of the formula (1), blue colorant, photopolymerizable compound, photopolymerization initiator in the obtained dispersion (hereinafter sometimes referred to as mill base) of the binder resin (mixture of cardo resin or cardo resin and acrylic alkali soluble resin) In addition, the other component used as needed, and an additional solvent can be further added as needed, and a desired blue photosensitive resin composition can be obtained as needed.

<Color filter and image display device>

Another aspect of the present invention relates to a color filter comprising a blue pattern layer containing a cured product of the blue photosensitive resin composition for forming a blue pattern layer described above.

Since the color filter according to the present invention is made of the blue photosensitive resin composition for forming the blue pattern layer instead of the blue quantum dots, there is an advantage of lowering the manufacturing cost. In addition, by including the thiol compound represented by the formula (1) in the blue photosensitive resin composition of the present invention, the blue photosensitive resin composition is a color excellent in excellent solvent resistance, adhesion and pattern formability (fine pattern formability) when forming a cured film Filter, self-luminous color filter may be implemented.

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

The substrate may be the substrate of the color filter itself, or may be a portion where the color filter is positioned 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).

The blue pattern layer is a layer including the blue photosensitive resin composition of the present invention, and may be a layer formed by applying the blue photosensitive resin composition for forming a blue pattern layer and exposing, developing and thermosetting in a predetermined pattern. Can be formed by carrying out methods commonly known in the art.

In another embodiment of the present 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 another embodiment of the present invention, the red pattern layer or green pattern layer may include a quantum dot and / or scattering particles. Specifically, the color filter according to the present invention may include a red pattern layer including a red quantum dot or a green pattern layer including a green quantum dot, and the red pattern layer or the green pattern layer may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light, respectively, by a light source emitting blue light, which will be described later.

In another embodiment of the present invention, the scattering particles included in the red pattern layer or the green pattern layer may include a metal oxide having an average particle diameter of 10 to 1000nm, the details of the scattering particles and the metal oxide The content of the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the invention can be applied.

In the present invention, the shape, configuration, and content of the quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art may be applied.

The color filter including the substrate and the pattern layer may further include a partition 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.

Another aspect of the invention, the above-described color filter; And a light source emitting blue light. In short, the image display apparatus according to the present invention includes a color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition and a light source emitting blue light.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

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

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Synthesis Example Synthesis of Binder Resin

Preparation Example 1: Acrylic Alkali Soluble Resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and vinyltoluene 118.0 g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, n-dodecanethiol 6g and PGMEA24g were added, and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 h each while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Started. Next, 28.4 g glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of acrylic acid used for this reaction)], 2,2'- methylenebis (4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were charged 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 weight average molecular weight of polystyrene conversion measured by GPC was 16,000, and molecular weight distribution (Mw / Mn) was 2.3.

Preparation Example 2 Synthesis of Compound of Formula 15

364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xantene) and 3-, 6'-dihydroxyspiro (fluorene-9,9-xantene) in a 3000 ml three-neck round flask 0.4159 g of bromide was mixed and 2359 g of epichlorohydrin was added and reacted by heating to 90 ° C. When the 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely consumed by liquid chromatography, 50% NaOH aqueous solution (3 equiv) was slowly added by cooling to 30 DEG C. After analysis by liquid chromatography, epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed three times, and then the organic layer was dried over magnesium sulfate. Then dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixture ratio of 50:50.

Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours 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 transparent compound of formula 15.

[Formula 15]

Preparation Example 3 Synthesis of Compound of Formula 16

364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xantene) and 3-, 6'-dihydroxyspiro (fluorene-9,9-xantene) in a 3000 ml three-neck round flask 0.4159 g of bromide was mixed and 2359 g of epichlorohydrin was added and reacted by heating to 90 ° C. When the 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely consumed by liquid chromatography, 50% NaOH aqueous solution (3 equiv) was slowly added by cooling to 30 DEG C. After analysis by liquid chromatography, epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed three times, and then the organic layer was dried over magnesium sulfate. Then dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixture ratio of 50:50.

Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid were mixed, and then 24.89 g of a solvent propylene glycol monomethyl ether acetate was added thereto. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours 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 transparent compound of formula 16.

[Formula 16]

Preparation Example 4 Synthesis of Compound of Formula 17

34.4 g of 4,4 '-(9H-xanthene-9,9-diyl) diphenol and 3-butylammonium bromide in a 3000 ml three-neck round flask 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the mixture was heated and reacted at 90 ° C. By liquid chromatography, 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenol) is completely depleted and cooled to 30 ℃. 50% NaOH aqueous solution (3 equiv) was added slowly. After epichlorohydrin was completely exhausted by liquid chromatography, the mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled under reduced pressure, and the mixture ratio of dichloromethane and methanol was 50:50. Recrystallized. Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto and mixed. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours 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 transparent compound of formula 17.

[Formula 17]

Preparation Example 5 Synthesis of Compound of Formula 18

34.4 g of 4,4 '-(9H-xanthene-9,9-diyl) diphenol and 3-butylammonium bromide in a 3000 ml three-neck round flask 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the mixture was heated and reacted at 90 ° C. By liquid chromatography, 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenol) is completely depleted and cooled to 30 ℃. 50% NaOH aqueous solution (3 equiv) was added slowly. After epichlorohydrin was completely exhausted by liquid chromatography, the mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled under reduced pressure, and the mixture ratio of dichloromethane and methanol was 50:50. Recrystallized. 1 equivalent of the epoxy compound thus synthesized, t-0.004 equivalent, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalent of methacrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto and mixed. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours 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 transparent compound of formula 1-2-2.

[Formula 18]

Preparation Example 6 Synthesis of Cardo-Based Binder Resin (A-1)

After dissolving by adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 15 of Preparation Example 2, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated up at 110 to 115 ° C. The reaction was carried out 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 with a cardo-based binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 3500

Preparation Example 7 Synthesis of Cardo-Based Binder Resin (A-2)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of Formula 16 in Preparation Example 3, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated up at 110 to 115 ° C. The reaction was carried out 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 with a cardo-based binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 3800

Preparation Example 8 Synthesis of Cardo-Based Binder Resin (A-3)

After dissolving by adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of Formula 17 of Preparation Example 3, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 4 at 110 to 115 ° C. The reaction was carried out for a time. 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 with a cardo-based binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 4500

Preparation Example 9 Synthesis of Cardo-Based Binder Resin (A-4)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of Formula 18 in Preparation Example 3, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 4 at 110 to 115 ° C. The reaction was carried out for a time. 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 with a cardo-based binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 4900

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: 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 number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Example

As follows, the present invention will be described in more detail based on Examples. However, the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover contains all changes within the meaning and range equivalent to the scope of the claims. In addition, "%" and "part" which show content below are mass references | standards unless there is particular notice.

Examples 1 to 5 and Comparative Examples 1 to 2: Preparation of blue photosensitive resin composition

According to the composition of Tables 1 to 2, blue photosensitive resin compositions of Examples 1 to 5 Comparative Examples 1 and 2 were prepared. (Table 1 shows the scattering particles, Table 2 shows the composition and content of the compositions of Examples and Comparative Examples.)

TABLE 1

TABLE 2

(Unit: weight%)

0) Colorant:

B-1: Fastogen Blue EP-7S (DCI): C.I. Pigment Blue 15: 6

B-2: Fastogen Blue 5424 (DCI): C.I. Pigment Blue 15: 4

V-1: Fastogen Super Violet 140V (DIC): C.I. Pigment Violet 23

1) Binder Resin:

A-1: Production Example 6,

A-2: Preparation Example 7,

A-3: Production Example 8,

A-4: Production Example 9,

A-5: mono (2-methacryloyloxyalkyl) ester

2) Photopolymerizable Compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

3) a thiol compound represented by Formula 1:

D-1: Trimethylolpropane tris (3-mercaptopropionate); TMMP-20P

D-2: Pentaerythritoltetrakis (3-mercaptopropionate); PEMP

4) Photoinitiator (D): IRGACURE® 907 (manufactured by BASF)

5) Solvent (E): Propylene glycol monomethyl ether acetate

Manufacture of color filter

Color filters were prepared using the blue photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2. That is, each of the blue photosensitive resin compositions was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Subsequently, a test photomask having a transmissive pattern of 20 mm x 20 mm square and a line / space pattern of 1 to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an atmospheric atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

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

Test Example 1. Solvent Resistance

The produced color filter was immersed in N-methylpyrrolidone solvent for 30 minutes, and the color change before and after evaluation was evaluated. Specifically, the solvent resistance was measured by using a colorimeter (Olympus, OSP-200) and chromaticity of the substrate produced in the color filter manufacturing and after immersing the substrate on which the color coordinate measurement is completed for 30 minutes in N-methylpyrrolidone solvent Color and transmittance were remeasured with a colorimeter (Olympus, OSP-200). ΔEab is a value required by the following saturation equation by the CIE 1976 (L *, a *, b *) spatial colorimeter. (Japanese Color Society New Colors Color Handbook (Showa 60) p.266).

At this time, the equation to be used is calculated by the following Equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, the smaller the color change value, it is possible to manufacture a highly reliable color filter . The results are shown in Table 3 below.

Equation (1): ΔEab ^* = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^(1/2)

Test Example 2 Adhesiveness

When the generated pattern was evaluated through an optical microscope, the degree of tearing was evaluated on the following pattern. The results are shown in Table 3 below.

○: No tearing on the pattern

△: 1 to 3 tears on the pattern

×: 4 or more tears on the pattern

TABLE 3

Test Example 3 Fine Pattern Measurement

The size of the pattern obtained through the line / space pattern mask designed to 100 μm of the color filters manufactured using the blue photosensitive resins prepared in Examples 1 to 5 and Comparative Examples 1 to 2 was measured by OM equipment (ECLIPSE LV100POL Nikon Corporation). The pattern size was measured through).

TABLE 4

When the difference between the design value of the line / space pattern mask and the measured value of the obtained fine pattern is 20 µm or more, it is difficult to implement the fine pixel, and a negative value means a threshold value that causes a process defect.

As can be seen in Table 4, the blue photosensitive of Examples 1 to 5 containing the thiol compound represented by the formula (1) compared to the blue photosensitive resin composition of Comparative Examples 1 to 2 not containing the thiol compound represented by the formula (1) The resin composition was confirmed that the fine pattern was formed well.

The blue photosensitive resin composition of the present invention comprises a thiol compound represented by the formula (1) in the blue photosensitive resin composition, so that the blue photosensitive resin composition has excellent solvent resistance, adhesiveness and pattern forming property when formed into a cured film. It is possible to implement a color filter having excellent fine pattern formability, particularly a self-luminous color filter.

Claims (15)

1. A blue photosensitive resin composition comprising a scattering particle, a thiol compound represented by the following Chemical Formula 1, a blue colorant, a binder resin, a cardo-based binder resin, a photopolymerizable compound, a photoinitiator, and a solvent.

   [Formula 1]

   

   (Formula 1, Z ₁ is a methylene group or a linear or branched alkylene group or alkylmethylene group having 2 to 10 carbon atoms, Y is a single bond, -CO-, -O-CO- or -NHCO-, n It is an integer of 3-10, X is a C2-C70 n-valent hydrocarbon group which may have one or more ether bonds, or n is 3 and X is a trivalent group represented by following General formula (2). )

   [Formula 2]

   

   (In Formula 2, Z ₂ , Z ₃ and Z ₄ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms, and "*" represents a bond).
2. The blue photosensitive resin composition of claim 1, wherein the thiol compound represented by Chemical Formula 1 includes at least one selected from the group consisting of compounds represented by Chemical Formulas 5 to 12:

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   [Formula 8]

   

   [Formula 9]

   

   [Formula 10]

   

   [Formula 11]

   

   [Formula 12]

   

   .
3. The blue photosensitive resin composition of claim 1, wherein the scattering particles include a metal oxide having an average particle diameter of 10 to 1000 nm.
4. The method of claim 1, wherein the scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO, Nb ₂ O ₃ , SnO and MgO Blue photosensitive resin composition containing 1 or more types selected from the group.
5. The blue photosensitive resin composition according to claim 1, wherein the blue photosensitive resin composition further comprises a purple colorant.
6. The blue photosensitive resin composition of claim 1, wherein the blue colorant comprises at least one of a blue pigment and a blue dye.
7. The blue photosensitive resin composition of claim 1, wherein the cardo-based binder resin includes at least one of compounds represented by the following Chemical Formulas 13-1 and 13-2.

   [Formula 13-1]

   

   [Formula 13-2]

   

   (In Formulas 13-1 and 13-2,

   R ₁ , R ₂ , R ₃ and R ₄ are each independently,

   

   Is;

   X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group, and R ₅ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
8. The compound represented by Formula 13-1 is any one or more of compounds represented by Formula 15 or Formula 16, and the compound represented by Formula 13-2 is any one of the compounds represented by Formula 17 or Formula 18. Blue photosensitive resin composition which is more than:

   [Formula 15]

   

   [Formula 16]

   

   [Formula 17]

   

   [Formula 18]

   

   .
9. The blue photosensitive resin composition of claim 1, wherein the blue photosensitive resin composition further comprises an acrylic alkali-soluble resin as a binder resin.
10. The blue photosensitive resin composition according to claim 1, wherein the photoinitiator is an acetophenone-based compound.
11. The method of claim 10, wherein the acetophenone-based compound is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1- The blue photosensitive resin composition selected from the group consisting of ions.
12. The color filter containing the blue pattern layer which consists of a blue photosensitive resin composition of any one of Claims 1-11.
13. The method according to claim 12,

    The color filter further includes one or more selected from the group consisting of a red pattern layer and a green pattern layer,

    The red pattern layer or the green pattern layer is a color filter comprising a quantum dot.
14. The color filter of claim 12, wherein the color filter is a self-luminous color filter.
15. A color filter according to claim 12; And

    And a light source emitting blue light.